Polyolefin polymer composition

ABSTRACT

The present disclosure is generally directed to polyolefin polymers, such as polypropylene homopolymers, and propylene-ethylene copolymers that have improved flow properties. In one embodiment, the polymers can be produced using a solid catalyst component that includes a) dissolving a halide-containing magnesium compound in a mixture, the mixture including an epoxy compound, an organic phosphorus compound, and a hydrocarbon solvent to form a homogenous solution; b) treating the homogenous solution with an organosilicon compound during or after the dissolving step; c) treating the homogenous solution with a first titanium compound in the presence of a first non-phthalate electron donor, and an organosilicon compound, to form a solid precipitate; and d) treating the solid precipitate with a second titanium compound in the presence of a second non-phthalate electron donor to form the solid catalyst component, where the process is free of carboxylic acids and anhydrides.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is the U.S. National Stage entry and claims priority toInternational Application Number PCT/US2018/060768 filed under thePatent Cooperation Treaty and having a filing date of Nov. 13, 2018,which claims priority to U.S. Provisional Application No. 62/585,137having a filing date of Nov. 13, 2017, all of which are herebyincorporated by reference herein in their entirety for all purposes.

BACKGROUND

Polyolefins are a class of polymers derived from simple olefins. Knownmethods of making polyolefins involve the use of Ziegler-Nattapolymerization catalysts. These catalysts polymerize olefin monomersusing a transition metal halide to provide a polymer with various typesof stereochemical configurations.

One type of Ziegler-Natta catalyst system comprises a solid catalystcomponent, constituted by a magnesium halide on which are supported atitanium compound and an internal electron donor compound. In order tomaintain high selectivity for an isotactic polymer product, internalelectron donor compounds can be added during catalyst synthesis. Theinternal donor can be of various types. Conventionally, when a highercrystallinity of the polymer is required, an external donor compound isalso added during the polymerization reaction.

During the past 30 years, numerous supported Ziegler-Natta catalystshave been developed which afford a much higher activity in olefinpolymerization reactions and much higher content of crystallineisotactic fractions in the polymers they produce. With the developmentof internal and external electron donor compounds, polyolefin catalystsystems are continuously renovated.

Catalyst morphology control is an important aspect of industrialpolyolefin plant operation. Catalyst morphology characteristicsinfluence polymer powder properties such as the bulk density,flowability, degassing and particle adhesion. Such properties greatlyinfluence plant operation efficiency. For example, unsuitable catalystmorphology may cause failure in polymer morphology control, which canlead to serious trouble in plant operation, such as fouling or sheeting.

In addition to catalyst morphology, catalyst lifetime or the ability ofa catalyst to remain active over prolonged periods of time can also beimportant in producing polymers with desired characteristics. Catalystswith extended lifetime, for instance, can produce polyolefin polymersand especially impact resistant polyolefin copolymers with improved andmore controlled properties.

Although great advances have been made in polyolefin polymerizationprocesses and in formulating new catalyst systems, further improvementsare needed. For instance, a need exist for a polymerization process forproducing polyolefin polymers with improved polymer flowability andhandling. For example, polymer flowability issues are particularlyprevalent when producing impact resistant polyolefin polymers that haveelastomeric properties.

SUMMARY

In general, the present disclosure is directed to producing polyolefinpolymers having improved flowability properties that are easier tohandle and transport. Polyolefin polymers with improved flow properties,for instance, can be produced utilizing a catalyst system that not onlyhas a prolonged and extended lifetime but can also produce polyolefinpolymers having improved morphology characteristics that translate intoa polymer resin that has better fluid-like properties and is easier tohandle. Through the process of the present disclosure, the efficiency ofthe polymer production process is greatly improved.

In one embodiment, for instance, the present disclosure is directed to apolymer composition comprising a propylene-ethylene copolymer that is inthe form of particles. The propylene-ethylene copolymer includespropylene as a primary monomer and contains ethylene in an amountgreater than about 5% by weight, such as in an amount greater than about8% by weight, such as in an amount greater than about 10% by weight, andgenerally in an amount less than about 45% by weight. Thepropylene-ethylene copolymer, for instance, can be a heterophasicpolymer and/or can have elastomeric properties. In accordance with thepresent disclosure, the propylene-ethylene copolymer particles can beformulated so as to have improved flow properties such that thecopolymer displays a Cup Test result of less than about 10 seconds. Forexample, the copolymer can display a Cup Test Index of 2 or less.

The propylene-ethylene copolymer can generally have a melt flow index ofgreater than about 10 g/10 min, such as greater than about 20 g/10 min,such as greater than about 30 g/10 min, such as greater than about 40g/10 min, such as greater than about 50 g/10 min and generally less thanabout 500 g/10 min.

In an alternative embodiment, the present disclosure is directed to apolymer composition containing a polyolefin polymer, such as apolypropylene polymer. The polypropylene polymer is in the form ofparticles. The particles can have a D50 particle size of from about 150microns to about 3000 microns, such as from about 450 microns to about1000 microns. In accordance with the present disclosure, the particleshave a particle morphology such that the particles have a B/L3 ofgreater than about 0.6, such as greater than about 0.68, such as greaterthan about 0.7, such as greater than about 0.8 and generally less thanabout 1. In addition, the polymer composition can have a relatively highbulk density. The bulk density, for instance, can be greater than about0.415 g/cm³, such as from about 0.42 g/cm³ to about 0.6 g/cm³.

The polymer particles can have a rounded shape and can be devoid ofagglomerates. In one embodiment, for instance, the polymer particles maycomprise microspheres.

Polyolefin polymers as described above, such as propylene-ethylenecopolymers and other polypropylene polymers, can be formed using variousprocesses. In one embodiment, for instance, the polyolefin polymer isproduced in the presence of a catalyst system that includes a solidcatalyst component combined with an aluminum compound, at least oneselectivity control agent, and optionally an activity limiting agent. Inone embodiment, the solid catalyst component comprises a reactionproduct of a magnesium compound with an epoxy compound. The solidcatalyst component can further include an organic phosphorous compound,a titanium compound, an organosilicon compound, and an internal electrondonor. The solid catalyst component can further include a supportivedonor. In one embodiment, the supportive donor comprises ethyl benzoate,while the internal electron donor comprises an aryl diester.

The present disclosure is also directed to a solid catalyst component.The solid catalyst component, in one embodiment, comprises:

a magnesium compound including a halide-containing magnesium compoundand a reaction product of a magnesium compound with an epoxy compound;

an organic phosphorus compound;

a titanium compound;

an organosilicon compound containing: Si—O, or O—Si—O groups;

an internal electron donor, the internal electron donor comprising anaryl diester, a 1,2-phenylene dibenzoate, a diether, a succinate, anorganic acid ester, a polycarboxylic acid ester, a polyhydroxy ester, aheterocyclic polycarboxylic acid ester, an inorganic acid ester, analicyclic polycarboxylic acid ester, a hydroxy-substituted carboxylicacid ester compound having 2 to 30 carbon atoms, or a compound having atleast one ether group and at least one ketone group, or mixturesthereof;

wherein the solid catalyst component is free of side reaction productsbetween a carboxylic acid or an anhydride thereof and a magnesiumcompound or a titanium compound, and

wherein the solid catalyst component has a particle size from about 5microns to about 70 microns (on a 50% by volume basis).

In another aspect, a catalyst system for use in olefinic polymerizationis provided, the catalyst system comprising the solid catalyst componentproduced by the process of any of the above processes, an organoaluminumcompound, and optionally, an organosilicon compound.

In any of the above catalyst system embodiments the organoaluminumcompound may be an alkyl-aluminum compound. For example, thealkyl-aluminum compound may be a trialkyl aluminum compound such astriethylaluminum, triisobutylaluminum, or tri-n-octylaluminum.

In another aspect, a process is provided for polymerizing orcopolymerizing a polypropylene monomer, the process may includecontacting an olefinic monomer, or a mixture of olefinic monomers withthe above catalyst system for forming a homopolymer of the olefinicmonomer or a co-polymer of a mixture of olefinic monomers.

Other features and aspects of the present disclosure are discussed ingreater detail below.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a microscopic view of the polymer produced with thecatalyst component of Example 5 (Comparative).

FIG. 2 shows a microscopic view of the polymer produced with thecatalyst component of Example 7.

FIG. 3 shows a microscopic view of the polymer produced with thecatalyst component of Example 9.

FIG. 4 shows a microscopic view of the polymer produced with thecatalyst component of Example 11.

FIG. 5 shows a microscopic view of the polymer produced with thecatalyst component of Example 13 (Comparative).

FIG. 6 shows a microscopic view of the polymer produced with thecatalyst component of Example 23.

FIG. 7 shows a microscopic view of the polymer produced with thecatalyst component of Example 34.

DETAILED DESCRIPTION

Before describing several exemplary embodiments, it is to be understoodthat the invention is not limited to the details of construction orprocess steps set forth in the following description. The invention iscapable of other embodiments and of being practiced or being carried outin various ways.

Reference throughout this specification to “one embodiment,” “certainembodiments,” “one or more embodiments” or “an embodiment” means that aparticular feature, structure, material, or characteristic described inconnection with the embodiment is included in at least one embodiment.Thus, the appearances of the phrases such as “in one or moreembodiments,” “in certain embodiments,” “in one embodiment” or “in anembodiment” in various places throughout this specification are notnecessarily referring to the same embodiment. Furthermore, theparticular features, structures, materials, or characteristics may becombined in any suitable manner in one or more embodiments.

Although reference herein is to particular embodiments, it is to beunderstood that these embodiments are merely illustrative of theprinciples and applications of the present invention. It will beapparent to those skilled in the art that various modifications andvariations can be made to the method and apparatus of the presentinvention without departing from the spirit and scope of the invention.Thus, it is intended that the present invention include modificationsand variations that are within the scope of the appended claims andtheir equivalents.

In general, the present disclosure is directed to polyolefin polymershaving improved flow properties. For example, the polyolefin polymerscan be produced in the form of particles that have fluid-like propertiesthat provide various advantages and benefits. The polymer particles, forinstance, improve process efficiency, reduce waste, and allow for thepolyolefin polymers to be easily handled and transported.

In accordance with the present disclosure, polyolefin polymer resins areproduced having improved flow properties by, in one embodiment,carefully controlling the particle morphology during polymerization. Inan alternative embodiment, the flow properties of the polyolefin polymercan be improved by utilizing a catalyst with an extended catalyticlifetime. Utilizing a catalyst with extended and robust activity hasbeen found to produce polyolefin polymers, particularly polypropylenerandom copolymers, that have a particle construction that prevents theparticles from agglomerating or otherwise sticking together forproviding the polymer resin with dramatically improved flow properties.As will be described in greater detail below, in one embodiment, thepolyolefin particles of the present disclosure are formed in thepresence of a Ziegler-Natta catalyst formed from a magnesium compound, atitanium compound, epoxy, and one or more internal electron donorsand/or supportive donors.

In one embodiment, a polypropylene polymer is formed in accordance withthe present disclosure having a controlled particle morphology. Inparticular, the polypropylene particles can be formed having a morerounded or spherical shape in conjunction with a relatively high bulkdensity that improves the polymer production process and dramaticallyimproves polymer flowability.

For example, in one embodiment, the polypropylene polymer particles havea D50 particle size of greater than about 400 microns, such as greaterthan about 500 microns, such as greater than about 600 microns, such asgreater than about 700 microns, and generally less than about 1500microns, such as less than about 1200 microns, such as less than about1000 microns. The polymer particles can have a rounded shape. Theparticle morphology, for instance, is such that the particles have anaspect ratio, such as a B/L3 value of greater than about 0.6, such asgreater than about 0.68, such as greater than about 0.7, such as greaterthan about 0.75, such as greater than about 0.8, and generally less thanabout 1. For instance, the polymer particles can be devoid ofagglomerations and can have a substantially spherical shape. In oneembodiment, for instance, the polymer particles form microspheres.

In addition to having a rounded shape, the polymer particles can alsohave a relatively high bulk density. The bulk density of the particles,for instance, can be greater than about 0.415 g/cm³. For instance, thebulk density of the polymer particles can be greater than about 0.42g/cm³, such as greater than about 0.44 g/cm³, such as greater than about0.46 g/cm³, such as greater than about 0.48 g/cm³. The bulk density isgenerally less than about 0.6 g/cm³.

The above particle shape and morphology has been found to improveflowability and handling of the polymer. In various embodiments, thepolymer can comprise a homopolymer or copolymer. The copolymer, forinstance, may comprise a propylene-ethylene random copolymer. In oneembodiment, the polymer particles are formed in a polymerization processusing a catalyst that has a rounded shape and improved morphology.

In addition to forming polymer particles having a desired size and shapeas described above, in an alternative embodiment, the flowability ofelastomeric polypropylene copolymers can be improved using the same orsimilar catalyst. Although unknown, it is believed that using a catalysthaving an extended lifetime or activity can facilitate the production ofa propylene random copolymer having rubber-like characteristics withexcellent flow properties. The propylene random copolymer, for instance,can be formed using multiple reactors, such as at least two differentreactors in order to produce a copolymer having elastomeric properties.Through the process of the present disclosure, the polypropylene randomcopolymer can be produced that not only easily transfers from a firstreactor to a second reactor, but can also be easily handled and removedfrom the final reactor due to the improvement in flowability.

For example, in one embodiment, the polypropylene random copolymer maycomprise a propylene-ethylene copolymer containing ethylene in an amountgreater than about 3% by weight, such as greater than about 5% byweight, such as in an amount greater than about 8% by weight, such as inan amount greater than about 10% by weight, and generally in an amountless than about 45% by weight. The propylene-ethylene random copolymercan be a heterophasic polymer that has elastomeric properties. Suchpolymers have excellent impact strength resistance but tend to haverather adverse flowability characteristics. Propylene-ethylenecopolymers made in accordance with the present disclosure, however, canhave flow properties such that the copolymer exhibits a Cup Test resultof less than about 10 seconds, such as less than about 9 seconds, suchas less than about 8 seconds. For example, the propylene-ethylenecopolymer can display a Cup Test Index of 2 or less. The Cup Test is amethod that measures powder flowability, especially of high rubbercontent polypropylene copolymer powders.

The propylene-ethylene copolymer can have a melt flow rate of from about1 g/10 min to about 1000 g/10 min. For instance, the copolymer can havea melt flow rate of greater than about 10 g/10 min, such as greater thanabout 20 g/10 min, such as greater than about 30 g/10 min, such asgreater than about 40 g/10 min, such as greater than about 50 g/10 min.The melt flow rate is generally less than about 500 g/10 min, such asless than about 400 g/10 min, such as less than about 300 g/10 min, suchas less than about 200 g/10 min. In one embodiment, the melt flow ratecan be from about 50 g/10 min to about 150 g/10 min.

Embodiments of Catalyst Systems Used to Produce Polyolefin Polymers

Described herein are Ziegler-Natta catalyst systems and supports forZiegler-Natta catalysts and methods of making the same. One aspect ofthe catalyst systems is a solid catalyst component containing ahalide-containing magnesium compound and titanium compound forpolymerizing an olefin, where the solid catalyst component hassubstantially spherical or spheroidal shape. The solid catalystcomponent can be used to form a competent Ziegler-Natta catalyst incombination with one or more external and/or internal electron donorsand an organoaluminum compound.

As used throughout this disclosure, the term “solid catalyst component”refers to a pre-catalyst containing a halide-containing magnesiumcompound and titanium compound, and optionally one or more internalelectron donors that are useful for forming a competent Ziegler-Nattacatalyst system upon combination with a main group metal alkyl.

In a typical manner of employing the Ziegler-Natta catalyst system, asolid catalyst component, an electron donor, and an organoaluminumcompound (a main group metal alkyl) form a slurry catalyst system, whichcan contain any suitable liquid such as an inert hydrocarbon medium.Examples of inert hydrocarbon media include aliphatic hydrocarbons suchas propane, butane, pentane, hexane, heptane, octane, decane, dodecaneand kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexaneand methylcyclopentane; aromatic hydrocarbons such as benzene, tolueneand xylene; halogenated hydrocarbons such as ethylene chloride andchlorobenzene; and mixtures thereof. The slurry medium can be hexane,heptane or mineral oil. The slurry medium can be different from thediluent used in forming the mixture from which the solid catalystcomponent is precipitated.

The herein described solid catalyst supports can be utilized in anysuitable Ziegler-Natta polymerization catalyst system. Ziegler-Nattacatalyst systems include a reagent or combination of reagents that arefunctional to catalyze the polymerization of 1-alkenes (α-olefins) toform polymers, typically with high isotacticity, when pro-chiral1-alkenes are polymerized. The term “Ziegler-Natta catalyst” refers toany composition having a transition metal and a main group metal alkylcomponent capable of supporting catalysis of 1-alkene polymerization.The transition metal component is typically a Group IV metal such astitanium, or vanadium, the main group metal alkyl is typically anorganoaluminum compound having a carbon-Al bond, and the electron donorcan be any of numerous compounds including aromatic esters,alkoxysilanes, amines and ketones can be used as external donors addedto the transition metal component and the main group metal alkylcomponent or an appropriate internal donor added to the transition metalcomponent and the main group metal alkyl component during synthesis ofthose components.

Described herein are methods of making a solid catalyst component foruse in a Ziegler-Natta catalyst, and the methods and catalysts are freeof carboxylic acid or anhydrides. By being free of the carboxylic acidsand/or anhydrides, the catalysts provide high activity due to absence ofside products of the reaction between the carboxylic acid and/oranhydride with the magnesium compounds and TiCl₄, that may otherwiseresult in the deactivation of active centers in polymerization process.

The catalyst/support morphology is a key factor to consider in anycommercial polymer production process. To control the catalyst/supportmorphology variable techniques and processes are used. One suchtechnique is to use a surfactant during the support formation.Surfactants are compounds that lower the surface tension (or interfacialtension) between two liquids or between a liquid and a solid.Surfactants are usually polar organic compounds, and they can be removedfrom the solid catalyst or can partly stay on the catalyst surface.Surfactants may also act as a supportive internal donor interacting withthe main internal donor or act as a negative component deactivatingcatalytic active center during the polymerization process.

In a first aspect, a process is provided for preparing a solid catalystcomponent for the production of a polyolefin, such as a polypropylene.The processes include dissolving a halide-containing magnesium compoundin a mixture, where the mixture includes epoxy compound, an organicphosphorus compound, and a first hydrocarbon solvent to form ahomogenous solution. The homogenous solution is then treated with afirst titanium compound in the presence of an organosilicon compound andoptionally with a non-phthalate electron donor and/or supportive donor,and, to form a solid precipitate. The solid precipitate is then treatedwith a second titanium compound in the presence of a non-phthalateelectron donor to form the solid catalyst component. The process is tobe conducted free of carboxylic acids and anhydrides. Additionally, thedissolving and treating of the homogeneous solution may be performedsequentially or simultaneously. Finally, the first and second titaniumcompounds are, independently, represented as:Ti(OR)_(g)X_(4-g)where each R is independently a C₁-C₄ alkyl; X is Br, Cl, or I; and g is0, 1, 2, 3, or 4.

The halide-containing magnesium compound, epoxy compound, and organicphosphorus compound are reacted in the presence of a hydrocarbonsolvent. The hydrocarbon solvent can include aromatic or non-aromaticsolvents or combinations thereof. In certain embodiments, the aromatichydrocarbon solvent is selected from toluene and C2-C20 alkylbenzene. Incertain embodiments, the nonaromatic hydrocarbon solvent is selectedfrom hexane and heptane. In an embodiment, the hydrocarbon solvent is amixture of toluene and hexane. In another embodiment, the hydrocarbonsolvent is a mixture of ethylbenzene and heptane. In certainembodiments, a ratio of the non-aromatic solvent to the aromatic solventis from 10:90 to 90:10 wt % or 30:70 to 70:30 wt % or 40:60 to 65:35 wt% or 50:50 to 45:55 wt %.

In a particular embodiment, the halide-containing magnesium compound,epoxy compound, and organic phosphorus compound are reacted in thepresence of an organic solvent at a first temperature from about 25 toabout 100° C. to form a homogenous solution. In another embodiment, thefirst temperature is from about 40 to about 90° C. or from about 50 toabout 70° C. In a certain embodiment, the molar ratio of the magnesiumcompound to alkylepoxide is from about 0.1:2 to about 2:0.1 or about1:0.25 to about 1:4 or about 1:0.9 to about 1:2.2. In a certainembodiment, the molar ratio of the magnesium compound to the Lewis baseis from about 1:0.1 to about 1:4 or 0.5:1 to 2.0:1 or 1:0.7 to 1:1.Without wishing to be bound by any theory, it is believed that a halogenatom is transferred from the magnesium compound to the epoxy compound toopen the epoxide ring and form an alkoxide magnesium species having abond between the magnesium atom and the oxygen atom of the newly formedalkoxide group. During this process the organic phosphorus compoundcoordinates to Mg atom of halide-containing magnesium compound andincreases the solubility of the magnesium-containing species present.

The process for preparing the solid catalyst component may also includeaddition of an organosilicon compound during, or after, the dissolutionof the magnesium compound (Mg-compound) in the organic solvent, alongwith the epoxy compound. The organosilicon compound may be a silane, asiloxane, or a polysiloxane. The organosilicon compound, in someembodiments, may be represented as Formula (II):R_(n)—Si(OR′)_(4-n)  (II).In Formula (II) each R may be H, alkyl, or aryl; each R′ may be H,alkyl, aryl, or —SiR_(n′)(OR′)_(3-n), where n is 0, 1, 2, or 3.

In some embodiments, the organosilicon is a monomeric or polymericcompound. The organosilicon compound may contain —Si—O—Si— groups insideof one molecule or between others. Other illustrative examples of anorganosilicon compound include polydialkylsiloxane and/ortetraalkoxysilane. Such compounds may be used individually or as acombination thereof. The organosilicon compound may be used incombination with aluminum alkoxides and a first internal donor. In someembodiments, polydimethylsiloxane and/or tetraethoxysilane may be used.

The aluminum alkoxide referred to above may be of formula Al(OR′)₃ whereeach R′ is individually a hydrocarbon with up to 20 carbon atoms. Thismay include where each R′ is individually methyl, ethyl, n-propyl,iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,neo-pentyl, etc. It is believed that the organosilicon compound reactswith the aluminum oxide during the catalyst component preparation,thereby forming compounds containing Al—O—Si—O linkages. Therefore,these compounds can be prepared before the catalyst component synthesisand added directly to the process.

The organosilicon compound helps to precipitate the solid catalystcomponent from the solution. It is believed that the Si—O groups fromthe organosilicon compound coordinate to Mg atoms of the Mg-compoundduring the precipitation of solid catalyst component, thereby leading toa desired catalyst component morphology. This type of coordination isusually weak. Therefore, during the treatment of the solid catalystcomponent with the second Ti-compound and the second non-phthalateinternal donor, they displace the organosilicon compound from the Mgcompound, providing the high activity catalyst component.

It is known that the precipitation of the solid catalyst component usingMg compounds in an epoxy medium containing anhydrides or organic acidsresult in the certain side products containing derivatives formed byinteraction of epoxy compounds with anhydrides or organic acids. Thesederivatives contain carbonyl groups coordinated strongly to Mg-atom andcan be present on the final catalyst component, and lead to deactivationthe catalyst active centers. The above catalyst systems, which are freeof organic acids and/or anhydrides, address these deficiencies of theearlier systems.

The halide-containing magnesium compound in the homogenous solution istreated with a titanium halide compound to form a solid precipitate. Thesolution can be heated and a surface modifier can be added to controlphase morphology. Also, when treating with a titanium halide compound, anon-phthalate electron donor is added. The electron donor changes theviscosity and polarity of the solution that effects on the morphologyprecipitated particles, in particular, particle size, particle shape andparticle density.

As noted above, the process is carried out in the presence ofnon-phthalate donors. In one embodiment, a supportive donor is used thatmay also be referred to as the first non-phthalate donor. The supportivedonor or first non-phthalate donor may be a diether, succinate, diester,oxygen-containing electron donor such as an organic ester, polyester,polyhydroxy ester, heterocyclic polyester, inorganic esters, alicyclicpolyester, and hydroxy-substituted esters having 2 to about 30 carbonatoms.

Illustrative first non-phthalate donors or supportive donors includemethyl formate; ethyl acetate; vinyl acetate; propyl acetate; octylacetate; cyclohexyl acetate; ethyl propionate; methyl butyrate; ethylvalerate; ethyl stearate; methyl chloroacetate; ethyl dichloroacetate;methyl methacrylate; ethyl crotonate; dibutyl maleate; diethylbutylmalonate; diethyl dibutylmalonate; ethyl cyclohexanecarboxylate;diethyl 1,2-cyclohexanedicarboxylate; di-2-ethylhexyl1,2-cyclohexanedicarboxylate; methyl benzoate; ethyl benzoate; propylbenzoate; butyl benzoate; octyl benzoate; cyclohexyl benzoate; phenylbenzoate; benzyl benzoate; methyl toluate; ethyl toluate; amyl toluate;ethyl ethylbenzoate; methyl anisate; ethyl anisate; ethylethoxybenzoate, γ-butyrolactone; δ-valerolactone; coumarine; phthalide;ethylene carbonate; ethyl silicate; butyl silicate;vinyltriethoxysilane; phenyltriethoxysilane; diphenyldiethoxysilane;diethyl 1,2-cyclohexanecarboxylate; diisobutyl1,2-cyclohexanecarboxylate; diethyl tetrahydrophthalate and nadic acid;diethyl ester; diethyl naphthalenedicarboxylate; dibutylnaphthlenedicarboxylate; triethyl trimellitate and dibutyl trimellitate;3,4-furanedicarboxylic acid esters; 1,2-diacetoxybenzene;1-methyl-2,3-diacetoxybenzene; 2-methyl-2,3-diacetoxybenzene;2,8-diacetoxynaphthalene; ethylene glycol dipivalate; butanediolpivalate; benzoylethyl salicylate; acetylisobutyl salicylate;acetylmethyl salicylate; diethyl adipate; diisobutyl adipate;diisopropyl sebacate; di-n-butyl sebacate; di-n-octyl sebacate; ordi-2-ethylhexyl sebacate. In some embodiments, the first non-phthalatedonor is methyl formate, butyl formate, ethyl acetate, vinyl acetate,propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate,methyl butyrate, ethyl butyrate, isobutyl butyrate, ethyl valerate,ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, ethylacrylate, methyl methacrylate, ethyl crotonate, ethylcyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propylbenzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenylbenzoate, benzyl benzoate, ethyl p-methoxybenzoate, methyl p-methylbenzoate, ethyl p-t-butyl benzoate, ethyl naphthoate, methyl toluate,ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethylanisate, or ethyl ethoxybenzoate.

The combination of different supportive donors or first internal donorsand solvents can be used to produce a catalyst component with differentmorphology: i.e. granular and/or spherical. In particular, a catalystcomponent with granular support may be produced using mono-ester as afirst internal donor with an aromatic or hydrocarbon solvent, whilespherical type catalyst components may be produced using two or threedifferent internal donors (e.g. mono-ester, dialkyl ether and acrylates)in a mixture of two solvents (aromatic and hydrocarbons).

In one embodiment, a supportive donor or first internal electron donoris used in conjunction with a second non-phthalate electron donor.Second non-phthalate electron donors may include compounds that aredifferent from the first non-phthalate electron donor and is a compoundthat is a diether, succinate, oxygen-containing electron donors such asorganic ester, polyester, polyhydroxy ester, heterocyclic polyester,inorganic esters, alicyclic polyester, and hydroxy-substituted estershaving 2 to about 30 carbon atoms, or a compounding having at least oneether group and at least one ketone group. In some embodiments, thesecond non-phthalate donor is selected from the group consisting oflinear of cyclic diethers, and non-phthalate aromatic diesters. Inanother embodiment, the second internal electron donor may be adibenzoate, a dialkylate, and/or diarylate.

Additional illustrative second non-phthalate electron donors mayinclude, alone or in combination with any of the above, compoundsrepresented by the following formulas:

where each of R¹ through R³⁴ is independently H, F, Cl, Br, I, OR³³,alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, or heteroarylalkyl; q is an integer from0 to 12, wherein R³³ is a alkyl or heteroalkyl. Other non-phthalatedonors may also include those as listed as internal electron donors inU.S. Pat. No. 9,045,570, incorporated by reference herein.

Examples of the halide-containing magnesium compounds include magnesiumchloride, magnesium bromide, magnesium iodide, and magnesium fluoride.In one embodiment, the halide-containing magnesium compound is magnesiumchloride.

Illustrative of the epoxy compounds include, but are not limited to,glycidyl-containing compounds of the Formula:

wherein “a” is from 1, 2, 3, 4, or 5, X is F, Cl, Br, I, or methyl, andR^(a) is H, alkyl, aryl, or cyclyl. In one embodiment, the alkylepoxideis epichlorohydrin. In some embodiments, the epoxy compound is ahaloalkylepoxide or a nonhaloalkylepoxide.

According to some embodiments, the epoxy compound is selected from thegroup consisting of ethylene oxide; propylene oxide; 1,2-epoxybutane;2,3-epoxybutane; 1,2-epoxyhexane; 1,2-epoxyoctane; 1,2-epoxydecane;1,2-epoxydodecane; 1,2-epoxytetradecane; 1,2-epoxyhexadecane;1,2-epoxyoctadecane; 7,8-epoxy-2-methyloctadecane; 2-vinyl oxirane;2-methyl-2-vinyl oxirane; 1,2-epoxy-5-hexene; 1,2-epoxy-7-octene;1-phenyl-2,3-epoxypropane; 1-(1-naphthyl)-2,3-epoxypropane;1-cyclohexyl-3,4-epoxybutane; 1,3-butadiene dioxide;1,2,7,8-diepoxyoctane; cyclopentene oxide; cyclooctene oxide; α-pineneoxide; 2,3-epoxynorbornane; limonene oxide; cyclodecane epoxide;2,3,5,6-diepoxynorbornane; styrene oxide; 3-methyl styrene oxide;1,2-epoxybutylbenzene; 1,2-epoxyoctylbenzene; stilbene oxide; 3-vinylstyrene oxide; 1-(1-methyl-1,2-epoxyethyl)-3-(1-methylvinyl benzene);1,4-bis(1,2-epoxypropyl)benzene;1,3-bis(1,2-epoxy-1-methylethyl)benzene;1,4-bis(1,2-epoxy-1-methylethyl)benzene; epifluorohydrin;epichlorohydrin; epibromohydrin; hexafluoropropylene oxide;1,2-epoxy-4-fluorobutane; 1-(2,3-epoxypropyl)-4-fluorobenzene;1-(3,4-epoxybutyl)-2-fluorobenzene; 1-(2,3-epoxypropyl)-4-chlorobenzene;1-(3,4-epoxybutyl)-3-chlorobenzene; 4-fluoro-1,2-cyclohexene oxide;6-chloro-2,3-epoxybicyclo[2.2.1]heptane; 4-fluorostyrene oxide;1-(1,2-epoxypropyl)-3-trifluorobenzene; 3-acetyl-1,2-epoxypropane;4-benzoyl-1,2-epoxybutane; 4-(4-benzoyl)phenyl-1,2-epoxybutane;4,4′-bis(3,4-epoxybutyl)benzophenone; 3,4-epoxy-1-cyclohexanone;2,3-epoxy-5-oxobicyclo[2.2.1]heptane; 3-acetylstyrene oxide;4-(1,2-epoxypropyl)benzophenone; glycidyl methyl ether; butyl glycidylether; 2-ethylhexyl glycidyl ether; allyl glycidyl ether; ethyl3,4-epoxybutyl ether; glycidyl phenyl ether; glycidyl 4-tert-butylphenylether; glycidyl 4-chlorophenyl ether; glycidyl 4-methoxyphenyl ether;glycidyl 2-phenylphenyl ether; glycidyl 1-naphthyl ether; glycidyl2-phenylphenyl ether; glycidyl 1-naphthyl ether; glycidyl 4-indolylether; glycidyl N-methyl-α-quinolon-4-yl ether; ethyleneglycoldiglycidyl ether; 1,4-butanediol diglycidyl ether;1,2-diglycidyloxybenzene; 2,2-bis(4-glycidyloxyphenyl)propane;tris(4-glycidyloxyphenyl)methane; poly(oxypropylene)triol triglycidylether; a glycidic ether of phenol novolac;1,2-epoxy-4-methoxycyclohexane;2,3-epoxy-5,6-dimethoxybicyclo[2.2.1]heptane; 4-methoxystyrene oxide;1-(1,2-epoxybutyl)-2-phenoxybenzene; glycidyl formate; glycidyl acetate;2,3-epoxybutyl acetate; glycidyl butyrate; glycidyl benzoate; diglycidylterephthalate; poly(glycidyl acrylate); poly(glycidyl methacrylate); acopolymer of glycidyl acrylate with another monomer; a copolymer ofglycidyl methacrylate with another monomer;1,2-epoxy-4-methoxycarbonylcyclohexane;2,3-epoxy-5-butoxycarbonylbicyclo[2.2.1]heptane; ethyl4-(1,2-epoxyethyl)benzoate; methyl 3-(1,2-epoxybutyl)benzoate; methyl3-(1,2-epoxybutyl)-5-pheylbenzoate; N,N-glycidyl-methylacetamide;N,N-ethylglycidylpropionamide; N,N-glycidylmethylbenzamide;N-(4,5-epoxypentyl)-N-methyl-benzamide; N,N-diglycylaniline;bis(4-diglycidylaminophenyl)methane; poly(N,N-glycidylmethylacrylamide);1,2-epoxy-3-(diphenylcarbamoyl)cyclohexane;2,3-epoxy-6-(dimethylcarbamoyl)bicycle[2.2.1]heptane;2-(dimethylcarbamoyl)styrene oxide;4-(1,2-epoxybutyl)-4′-(dimethylcarbamoyl)biphenyl;4-cyano-1,2-epoxybutane; 1-(3-cyanophenyl)-2,3-epoxybutane;2-cyanostyrene oxide; and6-cyano-1-(1,2-epoxy-2-phenylethyl)naphthalene.

As an example of the organic phosphorus compound, phosphate acid esterssuch as trialkyl phosphate acid ester may be used. Such compounds may berepresented by Formula:

wherein R₁, R₂, and R₃ are each independently selected from the groupconsisting of methyl, ethyl, and linear or branched (C₃-C₁₀) alkylgroups. In one embodiment, the trialkyl phosphate acid ester is tributylphosphate acid ester.

The halide-containing magnesium compound, epoxy compound, and organicphosphorus compound are contacted in the presence of a hydrocarbonsolvent. The hydrocarbon solvent can include aromatic or non-aromaticsolvents or combinations thereof. In certain embodiments, the aromatichydrocarbon solvent is selected from toluene and C₂-C₂₀ alkylbenzene. Incertain embodiments, the nonaromatic hydrocarbon solvent is selectedfrom hexane and heptane. In an embodiment, the hydrocarbon solvent is amixture of toluene and hexane. In another embodiment, the hydrocarbonsolvent is a mixture of ethylbenzene and heptane. In certainembodiments, a ratio of the non-aromatic solvent to the aromatic solventis from 10:90 to 90:10 wt % or 30:70 to 70:30 wt % or 40:60 to 65:35 wt% or 50:50 to 45:55 wt %.

In a particular embodiment, the halide-containing magnesium compound,epoxy compound, and organic phosphorus compound are contacted in thepresence of an organic solvent at a first temperature from about 25 toabout 100° C. to form a homogenous solution. In another embodiment, thefirst temperature is from about 40 to about 90° C. or from about 50 toabout 70° C. In a certain embodiment, the molar ratio of the magnesiumcompound to alkylepoxide is from about 0.1:2 to about 2:0.1 or about1:0.25 to about 1:4 or about 1:0.9 to about 1:2.2. In a certainembodiment, the molar ratio of the magnesium compound to the Lewis baseis from about 1:0.1 to about 1:4 or 0.5:1 to 2.0:1 or 1:0.7 to 1:1.Without wishing to be bound by any theory, it is believed that a halogenatom is transferred from the magnesium compound to the epoxy compound toopen the epoxide ring and form an alkoxide magnesium species having abond between the magnesium atom and the oxygen atom of the newly formedalkoxide group. The organic phosphorus compound functions to increasethe solubility of the magnesium-containing species present.

After formation, the homogenous solution can be optionally treated witha halogenating agent. The halogenating agent can be an organic orinorganic compound containing at least one halogen atom that can betransferrable to a magnesium atom. In particular embodiments, thehalogenating agent contains chlorine. In particular embodiments, thehalogenating agent is selected from arynoyl chlorides, alkanoylchlorides, and alkyl chlorides. In certain embodiments, the halogenatingagent is selected from benzoyl chloride, furoyl chloride, acetylchloride, linear or branched (C₁-C₆) alkyl chloride, and (C₁-C₆)alkanoyl chloride. In one embodiment, the halogenating agent may bephthaloyl chloride. In other embodiments, however, the catalystcomposition can be completely phthalate-free. In other embodiments, thehalogenating agent is selected from HCl, TiCl₄, R_(n)TiCl_(4-n), SiCl₄,R_(n)SiCl_(4-n), and R—AlCl_(4-n), wherein R represents an alkyl,cycloalkyl, aromatic or alkoxy, and n is a whole number satisfying theformula 0<n<4. In certain embodiments the ratio of halogenating agent tomagnesium compound is at least 1:1 mol ratio.

The molar ratio of the first titanium compound added to thehalide-containing magnesium compound may be from about 3:1 to about15:1, or from about 5:1 to about 10:1.

The magnesium-containing solution formed during the reaction of thehalide-containing magnesium compound, epoxy compound, organic phosphoruscompound and organosilicon compound can be in the form of dispersions,colloids, emulsions, and other two-phase systems. The homogenoussolution can be emulsified using conventional emulsion techniquesincluding one or more of agitation, stirring, mixing, high and/or lowshear mixing, mixing nozzles, atomizers, membrane emulsificationtechniques, milling sonication, vibration, microfluidization, and thelike.

The magnesium-containing species phase is dispersed within the solventphase. The size and shape of droplets forming the magnesium phase can becontrolled through a combination of adjusting the temperature, adjustingthe amount of solvent, adjusting the agitation energy, andincluding/excluding various additives, including the surface modifier.The temperature during the titanium compounds addition is from about−35° C. to about 15° C. After phase separation and/or titanium compoundaddition, the mixture is raised to a higher temperature. In oneembodiment, the higher temperature is from about 15° C. to about 100° C.In another embodiment, the temperature is from about 20° C. to about 90°C. or from about 50° C. to about 85° C. or from about 60° C. to 85° C.In an embodiment, while the mixture is between the lower and highertemperatures, a surface modifier is added to facilitate formation ofspherical droplets of the magnesium phase surrounded by the solventphase. That is, the addition of a surface modifier can assist incontrolling the morphology of the droplets of the magnesium phase.

During addition of the titanium halide compound to the magnesiumsolution which contains associated molecules or groups of molecules ofthe magnesium alkoxide with coordinated organic phosphorus compound,organosilicon compound and molecules of solvent, the reaction occursbetween the magnesium alkoxide and the titanium halide compound formingthe magnesium halide and complexes of the magnesium halide with titaniumhalide compound and the titanium alkoxide.

At the beginning of the reaction (usually at low temperature: (−35 to−20° C.)) the newly formed associated groups of the magnesium halidemolecules and complexes of the magnesium halide with titanium halidecompound and the titanium alkoxide are present in “oil phase-droplets”(higher viscosity liquid than other media (solvent) around). During thecontinuation of the reaction (the reaction temperature is raised to0-40° C.) the magnesium halide molecules and complexes of the magnesiumhalide with titanium halide compound and the titanium alkoxide in theoil phase are crystallized. The crystallization process is usuallycompleted at temperatures of 50-100° C. forming the solid intermediatecatalyst component.

The morphology of the solid intermediate catalyst component (and thecatalyst component) (particle size and shape) depends on many factorsincluding the polarity of solvent, presence of reagents to controlprecipitation, surfactants, additives and others.

In particular, the size and shape of droplets forming the magnesiumphase can be controlled through a combination of adjusting thetemperature, amount of solvent, adjusting the agitation energy, andincluding/excluding various additives, including the surface modifierand temperature of the precipitation.

The catalyst component morphology and catalyst performances aresufficiently controlled by addition of the supportive electron donor (ordonors). The supportive electron donor is an organic compound containingan oxygen atom and has the ability to coordinate to magnesium atoms ofmagnesium in “oil phase-droplets” and allows control of theprecipitation process of the solid catalyst component with desiredmorphology.

In one embodiment, the supportive electron donor only controls theprecipitation process and the catalyst component morphology and is notincorporated into the catalyst component.

In other embodiments, the supportive electron donor controls theprecipitation process and catalyst component morphology and isincorporated in the catalyst component. Therefore, the supportiveelectron donor and the electron donor can both define the catalystperformance in polymerization process. The supportive electron donorsare usually weaker than the electron donors.

The combination of the organosilicon compound and the supportiveelectron donor during the precipitation of the solid catalystintermediate allow to make the catalyst component with desired granularor spherical shape morphology.

The granular catalyst component morphology can be prepared with araspberry shape, rounded raspberry shape, rounded shape andsubstantially spherical shape (microspheres) by variation of theorganosilicon compounds, supportive electron donors and the conditionsof the precipitation of the solid catalyst intermediate. The particlesizes of the catalyst component are from about 5 microns to about 70microns (on a 50% by volume basis) and depend on the conditions of theprecipitation (temperature, agitation speed, solvent and others) andtype and amount of the supportive donor.

The supportive electron donor is selected from carboxylic monoestersmethyl formate, butyl formate, ethyl acetate, vinyl acetate, propylacetate, octyl acetate, cyclohexy acetate, ethyl propionate, methylbutyrate, ethyl butyrate, isobutyl butyrate, ethyl valerate, ethylstearate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate,methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate,methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octylbenzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethylp-methoxybenzoate, methyl p-methylbenzoate, ethyl p-t-butylbenzoate,ethyl naphthoate, methyl toluate, ethyl toluate, amyl toluate, ethylethylbezoate, methyl anisate, ethyl anisate, or ethyl ethoxybenzoate.

Combining the halide-containing magnesium compound, epoxy compound,organic phosphorus compound, titanium halide and hydrocarbon solventmight create an emulsion with two phases: the solvent phase and themagnesium-titanium oil phase and with proper selection of the solventand reagents. This process can be used to prepare a sphericalmorphology. Phase separation is accomplished by proper solventselection. Solvent selection involves considering one or more ofphysical properties differences in polarity, density, and surfacetension among others causing the separation between the solvent and themagnesium phase. Toluene is an organic solvent diluent that has beenused for the formation of solid titanium catalyst components; however,use of toluene does not always promote the formation of two phases.Also, it has been discovered that the use of other alkylbenzenecompounds, hexane, and heptane as a solvent or mixture of aromatic andhydrocarbons can be used and result in the formation of a solvent phaseand a magnesium phase. The two phases are maintained upon subsequentaddition of the titanium compound. The combination of two or moredifferent supportive donors allow producing the solid catalyst componentwith spherical types.

Di-(C₁-C₁₂)-alkylether in combination with acrylates (surface modifier)are used as the supportive electron donors to prepare the spherical typecatalyst component.

General examples of the surface modifier include polymer surfactants,such as polyacrylates, polymethacrylates, polyalkyl methacrylates, orany other surfactant that can stabilize and emulsify. Surfactants areknown in the art, and many surfactants are described in McCutcheon's“Volume I: Emulsifiers and Detergents”, 2001, North American Edition,published by Manufacturing Confectioner Publishing Co., Glen Rock, N.J.,and in particular, pp. 1-233 which describes a number of surfactants andis hereby incorporated by reference for the disclosure in this regard. Apolyalkyl methacrylate is a polymer that may contain one or moremethacrylate monomers, such as at least two different methacrylatemonomers, at least three different methacrylate monomers, etc. Moreover,the acrylate and methacrylate polymers may contain monomers other thanacrylate and methacrylate monomers, so long as the polymer surfactantcontains at least about 40% by weight acrylate and methacrylatemonomers.

Examples of monomers that can be polymerized using known polymerizationtechniques into polymer surfactants include one or more of an acrylate;tert-butyl acrylate; n-hexyl acrylate; methacrylate; methylmethacrylate; ethyl methacrylate; propyl methacrylate; isopropylmethacrylate; n-butyl methacrylate; t-butyl methacrylate; isobutylmethacrylate; pentyl methacrylate; isoamyl methacrylate; n-hexylmethacrylate; isodecyl methacrylate; lauryl methacrylate; stearylmethacrylate; isooctyl acrylate; lauryl acrylate; stearyl acrylate;cyclohexyl acrylate; cyclohexyl methacrylate; methoxyethyl acrylate;isobenzyl acrylate; isodecyl acrylate; n-dodecyl acrylate; benzylacrylate; isobornyl acrylate; isobornyl acrylate; isobornylmethacrylate; 2-hydroxyethyl acrylate; 2-hydroxypropyl acrylate;2-methoxyethyl acrylate; 2-methoxybutyl acrylate;2-(2-ethoxyethoxy)ethyl acrylate; 2-phenoxyethyl acrylate;tetrahydrofurfuryl acrylate; 2-(2-phenoxyethoxy)ethyl acrylate;methoxylated tripropylene glycol monacrylate; 1,6-hexanediol diacrylate;ethylene glycol dimethacrylate; diethylene glycol dimethacrylate;triethylene glycol dimethacrylate; polyethylene glycol dimethacrylate;butylene glycol dimethacrylate; trimethylolpropane-3-ethoxylatetriacrylate; 1,4-butanediol diacrylate; 1,9-nonanediol diacrylate;neopentyl glycol diacrylate; tripropylene glycol diacrylate;tetraethylene glycol diacrylate; heptapropylene glycol diacrylate;trimethylol propane triacrylate; ethoxylated trimethylol propanetriacrylate; pentaerythritol triacrylate; trimethylolpropanetrimethacrylate; tripropylene glycol diacrylate; pentaerythritoltetraacrylate; glyceryl propoxy triacrylate;tris(acryloyloxyethyl)phosphate; 1-acryloxy-3-methacryloxy glycerol;2-methacryloxy-N-ethyl morpholine; and allyl methacrylate, and the like.

In certain embodiments, the surface modifier is selected frompoly((C₁-C₆) alkyl) acrylate, a poly((C₁-C₆) alkyl) methacrylate, and acopolymer of poly((C₁-C₆) alkyl) acrylate and poly((C₁-C₆) alkyl)methacrylate. In embodiments, a ratio of the surface modifier tohalide-containing magnesium compound is from 1:10 to 2:1 wt % or from1:5 to 1:1 wt %.

Examples of polymer surfactants that are commercially available includethose under the trade designation VISCOPLEX® available from RohMaxAdditives, GmbH, including those having product designations 1-254,1-256 and those under the trade designations CARBOPOL® and PEMULEN®available from Noveon/Lubrizol.

The polymer surfactant is typically added in a mixture with an organicsolvent. When added as a mixture with an organic solvent, the weightratio of surfactant to organic solvent is from about 1:20 to about 2:1.In another embodiment, the weight ratio of surfactant to organic solventis from about 1:10 to about 1:1. In yet another embodiment, the weightratio of surfactant to organic solvent is from about 1:4 to about 1:2.

Treatment with the second titanium compound may include adding thesecond titanium halide compound and the second electron donor to asolution containing the precipitate to form a solid catalystcomposition, and then bringing a temperature of the solid catalystcomposition to from 80° C. to 150° C. and further treating with thesecond titanium compound to form the solid catalyst component. In oneembodiment, the treatment may include more than one second electrondonor. For example, a plurality of electron donors can be used duringtreatment with the second titanium compound. In another embodiment, thesecond titanium compound treatment includes the steps of filtering outthe precipitate, adding the second titanium compound and the secondelectron donor in a solvent to the precipitate to form a solid catalystcomposition, and bringing a temperature of the solid catalystcomposition to from 80° C. to 150° C. In another embodiment, the secondtitanium compound treatment includes the steps of adding the secondtitanium compound to a solution containing the precipitate; and thenbringing a temperature of the solid catalyst composition to from 80° C.to 150° C. and further treating with the second titanium compound andthe second electron donor to form the solid catalyst component.

Treatment with the second titanium compound may include adding thesecond titanium halide compound and the second electron donor to asolution containing the precipitate to form a solid catalystcomposition, and then bringing a temperature of the solid catalystcomposition to from 80° C. to 150° C. and further treating with thesecond titanium compound to form the solid catalyst component. Inanother embodiment, the second titanium compound treatment includes thesteps of filtering out the precipitate, adding the second titaniumcompound and the second electron donor in a solvent to the precipitateto form a solid catalyst composition, and bringing a temperature of thesolid catalyst composition to from 80° C. to 150° C. In anotherembodiment, the second titanium compound treatment includes the steps ofadding the second titanium compound to a solution containing theprecipitate; and then bringing a temperature of the solid catalystcomposition to from 80° C. to 150° C. and further treating with thesecond titanium compound and the second electron donor to form the solidcatalyst component.

During this treatment, the supportive electron donor partly or fully isremoved from the catalyst component and the electron donors adjust thecoordination to magnesium halides resulting in increased catalystactivity.

In one embodiment, for instance, a solid catalyst component can be madein accordance with the present disclosure by combining a magnesiumhalide, such as magnesium chloride with an epoxy compound. The epoxycompound, for instance, can be epichlorohydrin. The magnesium halide andthe epoxy compound can be combined together at a molar ratio of fromabout 0.5:1 to about 1:0.5, such as from about 0.8:1.2 to about 1.2:0.8.In one embodiment, for instance, the magnesium halide and the epoxycompound can be combined together in approximately a 1 to 1 molar ratio.The magnesium halide and epoxy compound can be combined together in thepresence of a phosphate such as tributyl phosphate and a solvent such astoluene. In addition, an aluminum alkoxide surfactant may be present,such as aluminum alkoxide/isopropoxide.

A monoester, such as ethylbenzoate and a silicate, such astetraethylorthosilicate can be added to the above composition inaddition to a titanium halide such as titaniumtetrachloride to cause aprecipitate to form. In one embodiment, complexes of the magnesiumhalide with the monoester, the titanium chloride can form includingCl₃—Ti—O—CH(CH₂Cl)₂.

The above precipitate can then be treated with a second internal donor,such as an aryl diester and optionally in the presence with a titaniumhalide. The resulting solid catalyst component can be washed and used asdesired.

In general, the resulting solid catalyst component contains a magnesiumhalide, a titanium halide, the first internal donor or supportive donor,and the second internal donor. In addition, the solid catalyst componentcan contain residual amounts of an aluminum alkoxide, the organosiliconcompound and the phosphorus compound. For example, the amount of thealuminum alkoxide and/or the organosilicon compound present in the finalcatalyst can be generally greater than about 0.001% by weight, such asgreater than about 0.01% by weight, such as greater than about 0.1% byweight and generally less than about 1% by weight, such as less thanabout 0.5% by weight, such as less than about 0.3% by weight. The solidcatalyst component can also contain the phosphorous compound generallyin an amount greater than about 0.1% by weight, such as in an amountgreater than about 0.2% by weight, such as in an amount greater thanabout 0.3% by weight, and generally less than about 1% by weight, suchas less than about 0.5% by weight.

In an alternative embodiment, especially in order to form sphericalparticles, the first internal electron donor may include not only amonoester but also a dialkyl ether. In addition, the first internalelectron donor can be combined into the catalyst composition with aspherical-promoting surfactant, such as an acrylate surfactant. In oneembodiment, for instance, the surfactant may comprise a polyalkylmethacrylate.

The solid catalyst component of the present disclosure is produced withmany beneficial properties and characteristics. For instance, in oneembodiment, the catalyst component can be made with a relatively highsurface area. For example, the BET surface area of the catalyst can begreater than about 100 m²/g, such as greater than about 200 m²/g, suchas greater than about 300 m²/g, such as greater than about 400 m²/g andgenerally less than about 700 m²/g, such as less than about 600 m²/g.

The catalyst system may contain at least one organoaluminum compound inaddition to the solid catalyst component. Compounds having at least onealuminum-carbon bond in the molecule can be used as the organoaluminumcompound. Examples of organoaluminum compounds include those of Formula:AlR_(n)X_(3-n)wherein, R independently represents a hydrocarbon group usually having 1to about 20 carbon atoms, X represents a halogen atom, and 0<n≤3.

Specific examples of the organoaluminum compounds include, but are notlimited to, trialkyl aluminums such as triethyl aluminum, tributylaluminum and trihexyl aluminum; trialkenyl aluminums such astriisoprenyl aluminum; dialkyl aluminum halides such as diethyl aluminumchloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkylaluminum sesquihalides such as ethyl aluminum sesquichloride, butylaluminum sesquichloride and ethyl aluminum sesquibromide; alkyl aluminumdihalides such as ethyl aluminum dichloride, propyl aluminum dichlorideand butyl aluminum dibromide; dialkyl aluminum hydrides such as diethylaluminum hydride and dibutyl aluminum hydride; and other partiallyhydrogenated alkyl aluminum such as ethyl aluminum dihydride, and propylaluminum dihydride.

The organoaluminum compound can be used in the catalyst system in anamount that the mole ratio of aluminum to titanium (from the solidcatalyst component) is from about 5 to about 1. In another embodiment,the mole ratio of aluminum to titanium in the catalyst system is fromabout 10 to about 700. In yet another embodiment, the mole ratio ofaluminum to titanium in the catalyst system is from about 25 to about400.

The catalyst system may contain one or more selectivity control agents(SCA) in addition to the solid catalyst component. In one embodiment,the selectivity control agent can comprise one or more organosiliconcompounds, such as one or more silane compounds. This organosiliconcompound can also function as an external electron donor. Theorganosilicon compound contains silicon having at least one hydrogenligand (hydrocarbon group). General examples of hydrocarbon groupsinclude alkyl groups, cycloalkyl groups, (cycloalkyl)methylene groups,alkene groups, aromatic groups, and the like.

The organosilicon compound, when used as an external electron donorserving as one component of a Ziegler-Natta catalyst system for olefinpolymerization, contributes to the ability to obtain a polymer (at leasta portion of which is polyolefin) having a controllable molecular weightdistribution and controllable crystallinity while retaining highperformance with respect to catalytic activity.

The organosilicon compound is used in the catalyst system in an amountsuch that the mole ratio of the organoaluminum compound to theorganosilicon compound is from about 2 to about 90. In anotherembodiment, the mole ratio of the organoaluminum compound to theorganosilicon compound is from about 5 to about 70. In yet anotherembodiment, the mole ration of the organoaluminum compound to theorganosilicon compound is from about 7 to about 35.

In one embodiment, the organosilicon compound is represented by Formula:R_(n)—Si(OR′)_(4-n)wherein each R and R′ independently represent a hydrocarbon group, and nis 0≤n<4.

Specific examples of the organosilicon compound include, but are notlimited to trimethylmethoxysilane, trimethylethoxysilane,dimethyldimethoxysilane, dimethyldiethoxysilane,diisopropyldimethoxysilane, diisobutyldimethoxysilane,t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane,t-amylmethyldiethoxysilane, dicyclopentyldimethoxysilane,diphenyldimethoxysilane, phenylmethyldimethoxysilane,diphenyldiethoxysilane, bis-o-tolydimethoxysilane,bis-m-tolydimethoxysilane, bis-p-tolydimethoxysilane,bis-p-tolydiethoxysilane, bisethylphenyldimethoxysilane,dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane,n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane,phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane,methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,t-butyltriethoxysilane, nbutyltriethoxysilane, iso-butyltriethoxysilane,phenyltriethoxysilane, γ-amniopropyltriethoxysilane,cholotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane,cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,2-norbornanetrimethoxysilane, 2-norboranetriethoxysilane,2-norboranemethyldimethoxysilane, ethyl silicate, butyl silicate,trimethylphenoxysilane, and methyltriallyloxysilane.

In another embodiment, the organosilicon compound is represented byFormula:SiRR′_(m)(OR″)_(3-m)

wherein, 0≤m<3, such as 0≤m<2; and R independently represents a cyclichydrocarbon or substituted cyclic hydrocarbon group. Specific examplesof the group R include, but are not limited to cyclopropyl; cyclobutyl;cyclopentyl; 2-methylcyclopentyl; 3-methylcyclopentyl;2-ethylcyclopentyl; 3-propylcyclopentyl; 3-isopropylcyclopentyl;3-butylcyclopentyl; 3-tertiary-butyl cyclopentyl;2,2-dimethylcyclopentyl; 2,3-dimethylcyclopentyl;2,5-dimethylcyclopentyl; 2,2,5-trimethylcyclopentyl;2,3,4,5-tetramethylcyclopentyl; 2,2,5,5-tetramethylcyclopentyl;1-cyclopentylpropyl; 1-methyl-1-cyclopentylethyl; cyclopentenyl;2-cyclopentenyl; 3-cyclopentenyl; 2-methyl-1-cyclopentenyl;2-methyl-3-cyclopentenyl; 3-methyl-3-cyclopentenyl;2-ethyl-3-cyclopentenyl; 2,2-dimethyl-3-cyclopentenyl;2,5-dimethyl-3-cyclopentenyl; 2,3,4,5-tetramethyl-3-cyclopentenyl;2,2,5,5-tetramethyl-3-cyclopentenyl; 1,3-cyclopentadienyl;2,4-cyclopentadienyl; 1,4-cyclopentadienyl;2-methyl-1,3-cyclopentadienyl; 2-methyl-2,4-cyclopentadienyl;3-methyl-2,4-cyclopentadienyl; 2-ethyl-2,4-cyclopentadienyl;2,2-dimethyl-2,4-cyclopentadienyl; 2,3-dimethyl-2,4-cyclopentadienyl;2,5-dimethyl-2,4-cyclopentadienyl;2,3,4,5-tetramethyl-2,4-cyclopentadienyl; indenyl; 2-methylindenyl;2-ethylindenyl; 2-indenyl; 1-methyl-2-indenyl; 1,3-dimethyl-2-indenyl;indanyl; 2-methylindanyl; 2-indanyl; 1,3-dimethyl-2-indanyl; 4,5,6,7-tetrahydroindenyl; 4,5,6, 7-tetrahydro-2-indenyl; 4,5,6,7-tetrahydro-1-methyl-2-indenyl; 4,5,6,7-tetrahydro-1,3-dimethyl-2-indenyl; fluorenyl groups; cyclohexyl;methylcyclohexyl; ethylcylcohexyl; propylcyclohexyl;isopropylcyclohexyl; n-butylcyclohexyl; tertiary-butyl cyclohexyl;dimethylcyclohexyl; and trimethylcyclohexyl.

In the Formula: SiRR′_(m)(OR″)_(3-m), R′ and R″ are identical ordifferent and each represents a hydrocarbon. Examples of R′ and R″ arealkyl, cycloalkyl, aryl and aralkyl groups having 3 or more carbonatoms. Furthermore, R and R′ may be bridged by an alkyl group, etc.General examples of organosilicon compounds are those of formula (VIII)in which R is cyclopentyl group, R′ is an alkyl group such as methyl orcyclopentyl group, and R″ is an alkyl group, particularly a methyl orethyl group.

Specific examples of organosilicon compounds of FormulaSiRR′_(m)(OR″)_(3-m) include, but are not limited to trialkoxysilanessuch as cyclopropyltrimethoxysilane, cyclobutyltrimethoxysilane,cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane,2,3-dimethylcyclopentyltrimethoxysilane,2,5-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane,2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane andfluorenyltrimethoxysilane; dialkoxysilanes such asdicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane,bis(3-tertiary-butylcyclopentyl)dimethoxysilane,bis(2,3-dimethylcyclopentyl)dimethoxysilane,bis(2,5-dimethylcyclopentyl)dimethoxysilane,dicyclopentyldiethoxysilane, dicyclobutyldiethoxysilane,cyclopropylcyclobutyldiethoxysilane, dicyclopentenyldimethoxysilane,di(3-cyclopentenyl)dimethoxysilane,bis(2,5-dimethyl-3-cyclopentenyl)dimethoxysilane,di-2,4-cyclopentadienyl)dimethoxysilane,bis(2,5-dimethyl-2,4-cyclopentadienyl)dimethoxysilane,bis(1-methyl-1-cyclopentylethyl)dimethoxysilane,cyclopentylcyclopentenyldimethoxysilane,cyclopentylcyclopentadienyldimethoxysilane, diindenyldimethoxysilane,bis(1,3-dimethyl-2-indenyl)dimethoxysilane,cyclopentadienylindenyldimethoxysilane, difluorenyldimethoxysilane,cyclopentylfluorenyldimethoxysilane and indenylfluorenyldimethoxysilane;monoalkoxysilanes such as tricyclopentylmethoxysilane,tricyclopentenylmethoxysilane, tricyclopentadienylmethoxysilane,tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane,dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane,cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane,cyclopentyldimethylethoxysilane,bis(2,5-dimethylcyclopentyl)cyclopentylmethoxysilane,dicyclopentylcyclopentenylmethoxysilane,dicyclopentylcyclopentenadienylmethoxysilane anddiindenylcyclopentylmethoxysilane; andethylenebis-cyclopentyldimethoxysilane.

In one embodiment, one or more selectivity control agents are present inthe catalyst system. Particularly preferred selectivity control agentsinclude dimethyldimethoxysilane, n-propyltrimethoxysilane,methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane,n-propyltriethoxysilane, bis(perhydroisoquinolino) dimethoxysilane,2,2,6,6-tetramethylpiperidine, or mixtures thereof.

In one embodiment, one or more selectivity control agents may be used inconjunction with an activity limiting agent (ALA). The activity limitingagent can be an aliphatic ester. The aliphatic ester may be a C₄-C₃,aliphatic acid ester, may be a mono- or a poly-(two or more) ester, maybe straight chain or branched, may be saturated or unsaturated, and anycombination thereof. The C₄-C₃₀ aliphatic acid ester may also besubstituted with one or more Group 14, 15 or 16 heteroatom containingsubstituents. Nonlimiting examples of suitable C₄-C₃₀ aliphatic acidesters include C₁₋₂₀ alkyl esters of aliphatic C₄₋₃₀ monocarboxylicacids, C₁₋₂₀ alkyl esters of aliphatic C₈₋₂₀ monocarboxylic acids, C₁₋₄allyl mono- and diesters of aliphatic C₄₋₂₀ monocarboxylic acids anddicarboxylic acids, C₁₋₄ alkyl esters of aliphatic C₅₋₂₀ monocarboxylicacids and dicarboxylic acids, and C₄₋₂₀ alkyl mono- or polycarboxylatederivatives of C₂₋₁₀, (poly)glycols or C₂₋₁₀₀ (poly)glycol ethers. In afurther embodiment, the C₄-C₃₀ aliphatic acid ester may be isopropylmyristate, di-n-butyl sebacate, (poly)(alkylene glycol) mono- ordiacetates, (poly)(alkylene glycol) mono- or di-myristates,(poly)(alkylene glycol) mono- or di-laurates, (poly)(alkylene glycol)mono- or di-oleates, glyceryl tri(acetate), glyceryl tri-ester of C₂₋₄₀aliphatic carboxylic acids, and mixtures thereof. In a furtherembodiment, the C₄-C₃₀ aliphatic ester is isopropyl myristate ordi-n-butyl sebacate.

In one embodiment, the ALA is a non-ester composition. As used herein, a“non-ester composition” is an atom, molecule, or compound that is freeof an ester functional group. In other words, the “non-estercomposition” does not contain the following functional group

In one embodiment, the non-ester composition may be a dialkyl diethercompound or an amine compound. The dialkyl diether compound can berepresented by the following formula,

wherein R¹R⁴ are independently of one another an alkyl, aryl or aralkylgroup having up to 20 carbon atoms, which may optionally contain a group14, 15, 16, or 17 heteroatom, provided that R′ and R² may be a hydrogenatom. Nonlimiting examples of suitable dialkyl ether compounds includedimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, methylbutyl ether, methyl cyclohexyl ether, 2,2-dimethyl-1,3-dimethoxypropane,2,2-diethyl-1,3-dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxy propane,2,2-diisobutyl-1,3-dimethoxy propane,2-ethyl-2-n-butyl-1,3-dimethoxypropane,2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane,2,2-dimethyl-1,3-diethoxypropane,2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2,2-dicyclopentyl-1,3-dimethoxypropane,2-n-propyl-2-cyclohexyl-1,3-diethoxypropane, and9,9-bis(methoxymethyl)fluorene. In a further embodiment, the dialkylether compound is 2,2-diisobutyl-1,3-dimethoxypropane.

In one embodiment, the non-ester composition is an amine compound.Nonlimiting examples of suitable amine compounds include 2,6-substitutedpiperidines such as 2,6-dimethylpiperidine and2,2,6,6-tetramethylpiperidine and 2,5-substituted piperidines. In afurther embodiment, the piperidine compound is2,2,6,6-tetramethylpiperidine.

For ALA's that contains more than one carboxylate groups, all thecarboxylate groups are considered effective components. For example, asebacate molecule contains two carboxylate functional groups isconsidered to have two effective functional molecules.

As described above, in one embodiment, the activity limiting agent is aC4 to C30 Aliphatic acid ester. Alternatively, the activity limitingagent may comprise a diether or a poly(alkene glycol) ester of a C4 toC30 aliphatic acid. Particular activity limiting agents that may beincorporated into the catalyst system include isopropyl myristate,di-n-butyl sebacate, ethyl 4-ethoxybenzoate, propoxylated (POE) cocofatty acid esters such as containing 10 to 20 mols of POE, apoly(ethylene)glycol coco fatty acid ester, or mixtures thereof.

An especially preferred combination of SCA/ALA components is a mixtureof an alkoxy silane selected from the group consisting ofdicyclopentyldimethoxysilane, methylcyclohexyl-dimethoxysilane, andn-propyltrimethoxysilane with an ester which is isopropyl myristate,di(n-butyl) sebacate, (poly)(ethylene glycol) monolaurate, (poly)alkeneglycol) dioleate, (poly)(ethylene glycol) methyl ether laurate, glyceryltri(acetate), or a mixture thereof.

Preferred SCA/ALA mixtures according to the invention are thosecomprising from 1 to 99.9, more preferably from 30 to 99, and mostpreferably from 50 to 98 equivalent percent of one or more ALAcompounds, and correspondingly from 99 to 0.1, more preferably from 70to 1, most preferably from 50 to 2 equivalent percent of one or morealkoxysilane compounds. Regardless of the foregoing range of components,it is to be understood by the skilled artisan that the normalizedpolymerization activity at an elevated temperature should be less thanthat obtainable at 67° C. and less than that obtainable if thealkoxysilane alone were employed alone in the same total SCA molaramount.

The total molar quantity of the SCA mixture employed in the presentinvention based on moles of transition metal is desirably from 0.1 to500, more desirably from 0.5 to 100 and most preferably from 1.0 to 50With respect to quantity of ALA, the corresponding molar ratio based ontransition metal is desirably from 1 to 10,000, preferably from 2 to1000, and most preferably from 5 to 100.

Catalyst particle morphology is indicative of the polymer particlemorphology produced therefrom. The three parameters of polymer particlemorphology (sphericity, symmetry and aspect ratio) may be determinedusing a Camsizer instrument marketed by Horiba Scientific. CamsizerCharacteristics:

Sphericity${{SPHT} = {\frac{4\pi\; A}{P^{2}} = {{Circula}\;{rity}\; 2\mspace{14mu}\left( {{ISO}\mspace{14mu} 9276\text{-}6} \right)}}},$where:

P is the measured perimeter/circumference of a particle projection; and

A is the measured area covered by a particle projection.

P is the measured perimeter/circumference of a particle projection; and

A is the measured area covered by a particle projection.

For an ideal sphere, SPHT is defined as 1. Otherwise, the value is lessthan 1.

The symmetry is defined as:

${Symm_{0,3}} = {\frac{1}{2}\left( {1 + {\min\left( \frac{r_{1}}{r_{2}} \right)}} \right)}$where, r₁ und r₂ are distance from the centre of area to the borders inthe measuring direction. For asymmetric particles Symm is less than 1.If the centre of the area is outside the particle, i.e.

${\frac{r_{1}}{r_{2}} < 0},$the Symm is less than 0.5

x_(Ma)=r₁+r₂, or “Symm,” is the minimum value of measured set ofsymmetry values from different directions.

Aspect Ratio:

${b/l_{0,2,3}} = \frac{x_{c\mspace{14mu}\min}}{x_{{Fe}\mspace{11mu}\max}}$where x_(c min) and X_(Fe max) out of the measured set of x_(c) andx_(Fe) values.

The catalyst morphology characteristics such as aspect ratio (“B/L3”)can be used for characterization of polymer morphology. In someprocesses, the aspect ratio is higher than 0.6, or higher than 0.7, orhigher than 0.8, or higher than 0.90.

The particle size of the resulting catalyst component can vary dependingupon the process conditions and the desired result. In general, the D₅₀particle size can be greater than about 5 microns, such as greater thanabout 10 microns, such as greater than about 20 microns, such as greaterthan about 30 microns, such as greater than about 40 microns, such asgreater than about 50 microns, such as greater than about 60 microns,and generally less than about 70 microns, such as less than about 50microns, such as less than about 30 microns, such as less than about 25microns.

Polymerization Processes

Polymerization of olefins can be carried out in the presence of thecatalyst systems as prepared and described above. Various differentolefins can be polymerized in accordance with the present disclosure.For example, catalyst systems of the present disclosure can be used topolymerize ethylene, propylene, and the like. The catalyst systems canalso be used to produce homopolymers and copolymers. Generally speaking,an olefin monomer, such as propylene, is contacted with the catalystsystem described above under suitable conditions to form desired polymerproducts. In one embodiment, preliminary polymerization described belowis carried out before the main polymerization. In another embodiment,polymerization is carried out without preliminary polymerization. In yetanother embodiment, the formation of a polypropylene-co-polymer iscarried out using at least two polymerization zones.

Of particular advantage, the catalyst component of the presentdisclosure is well suited for use in all different types ofpolymerization processes. For instance, the catalyst component of thepresent disclosure can be used in bulk loop polymerization processes,gas phase processes, and the like. The catalyst component can also beused in a slurry process.

In preliminary polymerization, the solid catalyst component is usuallyemployed in combination with at least a portion of the organoaluminumcompound. This may be carried out in the presence of part or the wholeof the organosilicon compound (external electron donor compound). Theconcentration of the catalyst system used in the preliminarypolymerization may be much higher than that in the reaction system ofthe main polymerization.

In preliminary polymerization, the concentration of the solid catalystcomponent in the preliminary polymerization is usually from about 0.01to about 200 millimoles, or from about 0.05 to about 100 millimoles,calculated as titanium atoms per liter of an inert hydrocarbon mediumdescribed below. In one embodiment, the preliminary polymerization iscarried out by adding propylene or a mixture of propylene with anotherolefin and the above catalyst system ingredients to an inert hydrocarbonmedium and polymerizing the olefins under mild conditions.

Specific examples of the inert hydrocarbon medium include, but are notlimited to aliphatic hydrocarbons such as propane, butane, pentane,hexane, heptanes, octane, decane, dodecane and kerosene; alicyclichydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane;aromatic hydrocarbons such as benzene, toluene and xylene; and mixturesthereof. In certain embodiments, a liquid olefin may be used in place ofpart or the whole of the inert hydrocarbon medium.

The olefin used in the preliminary polymerization may be the same as, ordifferent from, an olefin to be used in the main polymerization.

The reaction temperature for the preliminary polymerization issufficient for the resulting preliminary polymer to not substantiallydissolve in the inert hydrocarbon medium. In one embodiment, thetemperature is from about −20° C. to about 100° C. In anotherembodiment, the temperature is from about −10° C. to about 80° C. In yetanother embodiment, the temperature is from about 0° C. to about 40° C.

Optionally, a molecular-weight controlling agent, such as hydrogen, maybe used in the preliminary polymerization. The molecular weightcontrolling agent is used in such an amount that the polymer obtained bythe preliminary polymerization has an intrinsic viscosity, measured indecaliter at 135° C., of at least about 0.2 dl/g, or from about 0.5 to10 dl/g.

In one embodiment, the preliminary polymerization is carried out so thatfrom about 0.1 g to about 1,000 g of a polymer is formed per gram of thesolid catalyst component of the catalyst system. In another embodiment,the preliminary polymerization is carried out so that from about 0.3 gto about 500 g of a polymer is formed per gram of the solid catalystcomponent. If the amount of the polymer formed by the preliminarypolymerization is too large, the efficiency of producing the olefinpolymer in the main polymerization may sometimes decrease, and when theresulting olefin polymer is molded into a film or another article, fisheyes tend to occur in the molded article. The preliminary polymerizationmay be carried out batchwise or continuously.

After the preliminary polymerization conducted as above, or withoutperforming any preliminary polymerization, the main polymerization ofthe propylene is carried out in the presence of the above-describedpolymerization catalyst system formed from the solid catalyst component,the organoaluminum compound and the organosilicon compound (externalelectron donor compound).

Examples of other olefins that can be used in the main polymerizationwith propylene are α-olefins having 2 to 20 carbon atoms such asethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene,1-hexene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-decene,1-tetradecene, 1-eicosene, and vinylcyclohexane. In illustrativeprocesses, these α-olefins may be used individually or in anycombination.

In one embodiment, propylene is homopolymerized, or a mixed olefincontaining propylene as a main component is copolymerized. When themixed olefin is used, the proportion of propylene as the main componentis usually at least about 50 mole %, or at least about 70 mole %.

By performing the preliminary polymerization, the catalyst system in themain polymerization can be adjusted in the degree of activity. Thisadjustment tends to result in a powdery polymer having a high bulkdensity. Furthermore, when the preliminary polymerization is carriedout, the particles shape of the resulting polymer becomes spherical, andin the case of slurry polymerization, the slurry attains excellentcharacteristics while in the case of gas phase polymerization, thepolymer seed bed attains excellent characteristics. Furthermore, inthese embodiments, a polymer having a high stereoregularity index can beproduced with a high catalytic efficiency by polymerizing an α-olefinhaving at least 3 carbon atoms. Accordingly, when producing thepropylene copolymer, the resulting copolymer powder or the copolymerbecomes easy to handle.

In the copolymerization of the propylene, a polyunsaturated compoundsuch as conjugated diene or non-conjugated diene may be used as acomonomer. Examples of comonomers include styrene, butadiene,acrylonitrile, acrylamide, α-methyl styrene, chlorostyrene, vinyltoluene, divinyl benzene, diallyphthalate, alkyl methacrylates and alkylacrylates. In one embodiment, the comonomers include thermoplastic andelastomeric monomers. The main polymerization of an olefin is carriedout usually in the gaseous or liquid phase. In one embodiment,polymerization (main polymerization) employs a catalyst systemcontaining the solid catalyst component in an amount from about 0.001 toabout 0.75 millimoles calculated as Ti atom per liter of the volume ofthe polymerization zone, the organoaluminum compound in an amount fromabout 1 to about 2,000 moles per mole of titanium atoms in the solidcatalyst component, and the organosilicon compound in an amount fromabout 0.001 to about 10 moles calculated as Si atoms in theorganosilicon compound per mole of the metal atoms in the organoaluminumcompound. In another embodiment, polymerization employs a catalystsystem containing the solid catalyst component in an amount of from0.005 to about 0.5 milimoles calculated as Ti atom per liter of thevolume of the polymerization zone, the organoaluminum compound in anamount from about 5 to about 500 moles per mole of titanium atoms in thesolid catalyst component, and the organosilicon compound in an amountfrom about 0.01 to about 2 moles calculated as Si atoms in theorganosilicon compound per mole of the metal atoms in the organoaluminumcompound. In yet another embodiment, polymerization employs a catalystsystem containing the alkyl benzoate derivative in an amount from about0.005 to about 1 mole calculated as Si atoms in the organosiliconcompound per mole of the metal atoms in the organoaluminum compound.

When the organoaluminum compound and the organosilicon compound are usedpartially in the preliminary polymerization, the catalyst systemsubjected to the preliminary polymerization is used together with theremainder of the catalyst system components. The catalyst systemsubjected to the preliminary polymerization may contain the preliminarypolymerization product.

The use of hydrogen at the time of polymerization promotes andcontributes to control of the molecular weight of the resulting polymer,and the polymer obtained may have a high melt flow rate. In this case,the stereoregularity index of the resulting polymer and the activity ofthe catalyst system can be increased according to the above methods.

In one embodiment, the polymerization temperature is from about 20° C.to about 170° C. In another embodiment, the polymerization temperatureis from about 50° C. to about 165° C. In one embodiment, thepolymerization pressure is typically from atmospheric pressure to about100 kg/cm². In another embodiment, the polymerization pressure istypically from about 2 kg/cm² to about 50 kg/cm². The mainpolymerization may be carried out batchwise, semi-continuously orcontinuously. The polymerization may also be carried out in two or morestages under different reaction conditions.

The olefin polymer so obtained may be a homopolymer, a random copolymer,a block copolymer or an impact copolymer. The impact copolymer containsan intimate mixture of a polyolefin homopolymer and a polyolefin rubber.Examples of polyolefin rubbers include ethylene propylene rubber (EPR)such as ethylene propylene methylene copolymer rubber (EPM) and ethylenepropylene diene methylene terpolymer rubber (EPDM).

The olefin polymer obtained by using the catalyst system has a verysmall amount of an amorphous polymer component and therefore a smallamount of a hydrocarbon-soluble component. Accordingly, a film moldedfrom the resultant polymer has low surface tackiness.

The polyolefin obtained by the polymerization process is excellent inparticle size distribution, particle diameter and bulk density, and thecopolyolefin obtained has a narrow composition distribution. In animpact copolymer, excellent fluidity, low temperature resistance, and adesired balance between stiffness and elasticity can be obtained.

In one embodiment, propylene and an α-olefin having 2 or from about 4 toabout 20 carbon atoms are copolymerized in the presence of the catalystsystem described above. The catalyst system may be one subjected to thepreliminary polymerization described above. In another embodiment,propylene and an ethylene rubber are formed in two reactors coupled inseries to form an impact polymer.

The α-olefin having 2 carbon atoms is ethylene, and examples of theα-olefin having about 4 to about 20 carbon atoms are 1-butene,1-pentene, 4-methyl-1-pentene, 1-octene, 1-hexene, 3-methyl-1-pentene,3-methyl-1-butene, 1-decene, vinylcyclohexane, 1-tetradecene, and thelike.

In the main polymerization, propylene may be copolymerized with two ormore such α-olefins. For example, it is possible to copolymerizepropylene with ethylene and 1-butene. In one embodiment, propylene iscopolymerized with ethylene, 1-butene or ethylene and 1-butene.

Copolymerization of propylene and another α-olefin may be carried out intwo stages. The polymerization in a first stage may be thehomopolymerization of propylene or the copolymerization of propylenewith the other α-olefin. In one embodiment, the amount of the monomerspolymerized in the first stage is from about 50 to about 95% by weight.In another embodiment, the amount of the monomers polymerized in thefirst stage is from about 60 to about 90% by weight. This first stagepolymerization may be carried out in two or more stages under the sameor different polymerization conditions.

In one embodiment, the polymerization in a second stage is carried outsuch that the mole ratio of propylene to the other α-olefin(s) is fromabout 10/90 to about 90/10. In another embodiment, the polymerization ina second stage is carried out such that the mole ratio of propylene tothe other α-olefin(s) is from about 20/80 to about 80/20. In yet anotherembodiment, the polymerization in a second stage is carried out suchthat the mole ratio of propylene to the other α-olefin(s) is from about30/70 to about 70/30. Producing a crystalline polymer or copolymer ofanother α-olefin may be provided in the second polymerization stage.

The propylene copolymer so obtained may be a random copolymer or theabove described block copolymer. The propylene copolymer can containfrom about 7 to about 50 mole % of units derived from the α-olefinhaving 2 or from about 4 to about 20 carbon atoms. In one embodiment, apropylene random copolymer contains from about 7 to about 20 mole % ofunits derived from the α-olefin having 2 or from about 4 to about 20carbon atoms. In another embodiment, the propylene block copolymercontains from about 10 to about 50 mole % of units derived from theα-olefin having 2 or 4-20 carbon atoms.

In another embodiment, copolymers made with the catalyst system containfrom about 50% to about 99% by weight poly-α-olefins and from about 1%to about 50% by weight comonomers (such as thermoplastic or elastomericmonomers). In another embodiment, copolymers made with the catalystsystem contain from about 75% to about 98% by weight poly-α-olefins andfrom about 2% to about 25% by weight comonomers.

In one embodiment, a two stage reactor system, such as two fluidized bedreactors in series, can be used to produce a polypropylene copolymerthat is heterophasic. For example, in one embodiment, a polypropylenehomopolymer or polypropylene random copolymer of a first phase isprepared in a first stage reactor. The first phase can comprise acontinuous polymer phase in the resulting polymer. An elastomericpropylene copolymer is then produced in a second stage and forms thesecond phase. The first stage polymerization can be carried out in oneor more bulk reactors or in one or more gas phase reactors. The secondstage polymerization can be carried out in one or more gas phasereactors. The second stage polymerization is typically carried outdirectly following the first stage polymerization. The resultingheterophasic copolymer, which can comprise a propylene-ethylenecopolymer, can have excellent impact resistance properties and haveelastomeric properties.

The catalyst as described above is particularly well suited for use inproducing polypropylene polymers in two stage reactors. The catalyst,for instance, has been found to have a dramatically prolonged lifetimeand therefore maintains high catalyst activity levels within the secondreactor. It is believed that the increased lifetime of a catalyst helpsto produce polymer resins with better flow properties.

In one embodiment, the catalyst efficiency (measured as kilogram ofpolymer produced per gram of catalyst) of the catalyst system is atleast about 30 kg/g/h. The catalyst deficiency, for instance, can behigher than about 60 kg/g/h, such as greater than about 80 kg/g/h, suchas greater than about 100 kg/g/h, such as greater than about 140 kg/g/h.

The catalysts/methods discussed above can in some instances lead to theproduction of poly-α-olefins having melt flow rates (“MFR”, g/10minutes) from about 0.01 to about 500 g/10 min, such as from about 0.1to about 400 g/10 min. In another embodiment, poly-α-olefins having anMFR from 0.1 to about 300 are produced.

In addition to the melt flow rate, the polydispersity index (PI) canvary depending upon various factors and the desired result. Thepolydispersity index can generally be greater than about 3, such asgreater than about 5, and generally less than about 8, such as less thanabout 6.

The catalysts/methods described above can in some instances lead to theproduction of poly-α-olefins having bulk densities (BD) of at leastabout 0.35 cc/g. In another embodiment, poly-α-olefins having a BD of atleast about 0.4 cc/g are produced. In one embodiment, for instance,polypropylene polymers can be produced having a relatively high bulkdensity. The bulk density, for instance, can be greater than 0.415g/cm³, such as greater than 0.42 g/cm³, such as greater than 0.44 g/cm³′such as greater than 0.46 g/cm³. The bulk density is generally less thanabout 0.8 g/cm³, such as less than about 0.6 g/cm³.

The catalysts/methods described above can lead to the production ofpoly-α-olefins having a Span of less than 1.0. In some embodiments, theSpan is less than 0.6.

Embodiments of the present invention can lead to the production of apropylene block copolymer and impact copolymers including polypropylenebased impact copolymer having one or more excellent melt-flowability,moldability, desirable balance between rigidity and elasticity, goodstereospecific control, good control over polymer particle size, shape,size distribution, and molecular weight distribution, and impactstrength with a high catalytic efficiency and/or good operability.Employing the catalyst systems containing the solid catalyst componentaccording to embodiments of the present invention yields catalystssimultaneously having high catalytic efficiency, and one or more ofexcellent melt-flowability, extrudability, moldability, rigidity,elasticity and impact strength.

The following examples illustrate embodiments of the present invention.Unless otherwise indicated in the following examples and elsewhere inthe specification and claims, all parts and percentages are by weight,all temperatures are in degrees Celsius, and pressure is at or nearatmospheric.

EXAMPLES Abbreviations and Definitions

“D₁₀” represents the size of particles (diameter), wherein 10% ofparticles are less than that size, “D₅₀” represents the size ofparticles, wherein 50% of particles are less than that size, and “D₉₀”represents the size of particles, wherein 90% of particles are less thanthat size. “Span” represents the distribution of the particle sizes ofthe particles. The value can be calculated according to the followingformula:Span=(D ₉₀ −D ₁₀)D ₅₀“PP” prior to any D or Span value indicates the D value or Span valuefor polypropylene prepared using the catalysts indicated unlessotherwise specified, all values are in microns.

BD is an abbreviation for bulk density, and is reported in units of g/mlor g/cm³. To measure bulk density, the polymer is dried in an oven at60° C. for one hour and then cooled to room temperature beforemeasurement. A cylindrical measuring cup is used that is 9½ inches inheight and has an inside diameter of 1.8 inches. The measuring cup has avolume of 395 ml. A funnel having a 1 inch diameter opening at thebottom is mounted 1½ inches above the measuring cup. The small end ofthe funnel is covered with a straight edge. 500 ml of polymer sample isloaded into the funnel. The straight edge is then quickly removed whichallows the polymer sample to flow into the measuring cup. Immediatelyafter flow of the polymer into the cup has stopped, a straight edge isused to remove excess sample from the top of the measuring cup. The bulkdensity is equal to the net sample mass divided by 395 ml.

CE is an abbreviation for catalyst efficiency and is reported in unitsof Kg polymer per gram of catalyst (Kg/g) during the polymerization for1 hour.

MFR is an abbreviation for melt flow rate and is reported in units ofg/10 min. The MFR is measured according to ASTM test number D1238 at230° C. with a 2.16 kg load.

The catalyst component particle size analysis was conducted using laserlight scattering method by Malvern Mastersizer 3000 instrument. Tolueneused as a solvent.

The surface area and pore size distribution of the catalyst componentswere measured by Micrometrics ASAP 2020 instrument. The catalystcomponent samples were degassed by heating at 60° C. under vacuum forfew hours before the measurement.

The polydispersity index (PI) and zero shear viscosity for polymersamples were obtained from rheological data by ARES G2 Rheometer. Thestabilized polymer sample is pressed on hot press to make plate. Thepolymer plate is then analyzed on the Rheometer. From the data plot PIand zero shear viscosity are calculated using built in MWD software.

The Cup Test is a method to measure polymer powder flowability. The testis particularly well suited to measuring the flowability of high rubbercontent polypropylene impact copolymers. The test is especially usefulwhen polymer resins are sticky making angle of repose measurementsunreliable. The method includes filling a polystyrene 12 oz, coffee cupwith the polymer resin powder. The cup is filled with the polymer resinand a flat edge is used to remove excess. The cup is then inverted on aflat surface for 30 minutes. The cup is then removed and a testerobserves the shape of the powder and how long it takes to deform andcollapse from the initial cup shape. The Cup Test can be measured inseconds for the powder to collapse. The Cup Test also includes a CupTest Index as specified below:

Cup Test Index Powder Shape Retention Time 0 Immediately loses its shape1 1 second to lose its shape 2 15 seconds to lose its shape 3 1 minuteto lose iths shape 4 Indefinite-needs some agitation to lose its shape 5Indefinite-needs considerable agitation to make it lose its shape 6Indefinite-needs aggressive agitation to make it lose its shape 7 Never

NPDE is an abbreviation for a non-phthalate diaryl ester and can be ofthe formula:

where R¹-R4-selected from substituted or unsubstituted aryl groups,R³R⁴R⁵R⁶ are the same or different alkyl or cycloalkyl having 1 to 20carbon atoms, heteroatom or combination of them. As used herein, NPDE1is 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate. NPDE2, on the otherhand, is described in paragraph 52 of U.S. Patent Publication US2013/0261273, which is incorporated herein by reference.

SYLTHERM is a tradename for a polydimethyl siloxane (PDMS) that iscommercially available from Dow Chemical.

VISCOPLEX is a tradename for a polyalkyl methacrylate available fromEvonik.

EB is an abbreviation for ethyl benzoate.

TBP is an abbreviation for tributyl phosphate.

ECH is an abbreviation for epichlorohydrin.

TEOS is an abbreviation for tetraethylorthosilicate.

Ti, Mg, and D are the weight percentages (wt %) for each of thetitanium, magnesium, and internal donor (NPDE), respectively, in thecomposition.

XS is an abbreviation for xylene solubles, and is reported in units ofwt %.

Bulk Propylene Polymerization

Where catalysts of the examples are used in a method of propylenepolymerization the following method was used. The reactor was baked at100° C. under nitrogen flow for 30 minutes prior to the polymerizationrun. The reactor was cooled to 30-35° C. and cocatalyst (1.5 ml of 25 wt% triethylaluminum (TEA1)), C-donor [cyclohexylmethydimethoxysilane] (1ml), hydrogen (3.5 psi) and liquid propylene (1500 ml) were added inthis sequence into the reactor. The catalyst (5-10 mg), loaded as amineral oil slurry, was pushed into the reactors using high pressurenitrogen. The polymerization was performed for one hour at 70° C. Afterthe polymerization, the reactors were cooled to 22° C., vented toatmospheric pressure, and the polymer collected.

Gas Phase Propylene Polymerization

Where catalysts of the examples are used in a method of propylenepolymerization the following method was used. The reactor was baked at100° C. under nitrogen flow for 30 minutes prior to the polymerizationrun. The reactor was cooled to 30° C. and propylene was charged (120 g),with cocatalyst (0.27 ml of 25 wt % triethylaluminum (TEA1)), C-donor[cyclohexylmethydimethoxysilane] (0.38 ml), and hydrogen (0.5 g). Areactor was heated to 35° C. and the catalyst component (0.5-0.7 mg) wasflashed to the reactor with propylene (120 g). The polymerization wasperformed for one hour at 70° C. After the polymerization, the reactorswere cooled to 22° C., vented to atmospheric pressure, and the polymercollected.

Examples 1-3 illustrates preparing the catalyst components using anorganosilicon compound without supportive donor and provides theproperties of polymer produced using a bulk propylene polymerizationscheme.

Example 1 demonstrates preparing the catalyst component usingtetraethylorthosilicate. The catalyst produced polymer with raspberryshape particle morphology with BD below 0.40 g/cc and B/L3<0.7

3.3 g of MgCl₂, 20 g toluene, 6.7 g TBP, 6.43 g of ECH was charged toreactor. The mixture was heated to 60° C. and held for 8 hours at 600RPM agitation speed. The mixture was allowed to cool to 25°. 27 grams oftoluene and 1.5 grams of tetraethylorthosilicate in 3 grams toluene wereadded to the reactor at 25° C. The reactor was cooled to −25° C. and65.2 grams of TiCl₄ was added. After the addition, the stirring rate wasdropped to 200 rpm and the reaction was heated to 35° C. for over twohours and held for 30 minutes, heated to 85° C. for 30 minutes and heldfor 30 minutes. Filter. The reaction was washed with 50 mL of toluene,3×. 65 ml of toluene was added and the reactor was heated to 40° C. @400 RPM. 0.64 grams of NPDE1 was added and the reactor was heated up to105° C. and held for one hour. Filter. 65 mL of 10% TiCl₄ was added andthe temperature raised to 105° C. for one hour. Filter. 65 mL of 10%TiCl₄ was added and the temperature raised to 110° C. for 30 minutes andfiltered 3 times. The solid was washed with 50 mL of hexanes @ 65° C.and 400 RPM 3 times. The catalyst component was discharged as a hexaneslurry. The analytical data and the catalyst performance is presentedbelow.

Example 2 demonstrates the catalyst component using two organosiliconcompounds (tetraethylorthosilicate and Syltherm PDMS) and Al(OiPr)3. Theinternal donor was added in two places: in before the solid formed andto the solid component. The catalyst produced polymer with roundedraspberry type morphology and improved bulk density (BD=0.44 g/cc).

3.3 g of MgCl₂ to correct subscript, 0.25 g Al(O-iPr)3, 20 g toluene,9.1 g TBP, 1.0 g Syltherm(PDMS), 3.55 g of ECH was charged to reactor.The mixture was heated to 60° C. and held for 8 hours at 600 RPMagitation speed. The mixture was allowed to cool to 25° C. 27 grams oftoluene, 1.5 grams of TEOS in 3 grams of toluene, and 0.64 grams ofNPDE1 were added the reactor. The reactor was chilled to −25° C. and65.4 grams of TiCl₄ was added to the reactor. The agitation was set to300 RPM and ramped to 35° C. over 2 hours. The reaction was held at 35°C. for 30 minutes @ 300 RPM. The reaction was heated to 85° C. and heldfor 30 minutes. The reaction was filtered and 50 mL of toluene wasadded. The reactor was heated to 40° C. @ 400 RPM and 0.64 grams ofNPDE1 was added. The reactor continued heating to 105° C. and was heldfor 1 hour, then allowed to settle and decanted. 65 mL of 10% TiCl₄ wasadded, heated to 105° C. and held for 1 hour. The reaction was allowedto settle and it was decanted. 65 mL of 10% TiCl₄ was added, heated to110° C. and held for 1 hour. The reaction was allowed to settle and itwas decanted. 50 mL of hexane was added and stirred for 5 minutes @jacket temperature of 65° C. The reaction was allowed to settle and wasdecanted. Hexane was then added and the product was discharged as ahexane slurry.

Example 3 demonstrates the catalyst component using two organosiliconcompounds (tetraethylorthosilicate and Syltherm PDMS) and Al(OiPr)3. Theinternal donor was added to the solid component. The particle size ofcatalyst component increased to 14 microns (compared with examples 1 and2).

3.3 g of MgCl₂, 0.25 g Al(O-iPr)3, 20 g toluene, 6.7 g TBP, 1.0 gSyltherm(PDMS), 6.43 g of ECH was charged to the reactor. The mixturewas heated to 60° C. and held for 8 hours @ 600 RPM agitation speed. Themixture was allowed to cool to 25° C. 27 grams of toluene, 1.5 grams ofTEOS in 3 grams of toluene were added to reactor at 600 rpm and 25° C.The reactor was cooled to −25° C. and 65.2 grams of TiCl₄ was added. Thereactor was heated to 35° C. @ 200 RPM for over two hours and held at35° C. for 30 minutes; heated to 85° C. over 30 minutes and held at 85°C. for 30 minutes and decanted washed 3× with toluene. Cool to 25° C.and let sit over weekend. Filter, add 65 mL of toluene. Heat to 40° C. @400 RPM and add 0.64 grams NPDE1. Heat to 105° C. for one hour. Filter.Add 65 mL of 10% TiCl₄, heat to 105° C., hold for one hour. Filter. Add65 mL of 10% TiCl₄, heat to 110° C., hold for one hour. Filter. Washwith 50 mL of hexanes 3×, jacket temperature @ 65, agitate 5 minutesbetween washes. Discharge as hexane slurry.

Example 4 (Comparative)

This example demonstrates preparing the catalyst component withoutorganosilicon compound. The catalyst produced polymer with irregularmorphology with agglomerated polymer particles.

3.3 g of MgCl₂, 1.15 g Al(O-iPr)3, 20 g toluene, 6.7 g TBP, 6.43 g ofECH was charged to reactor 14A. The mixture was heated to 60° C. andheld for 8 hours @ 600 RPM agitation speed. The mixture was allowed tocool to 25° C. 30 grams of toluene was added to the reactor at 25° C.and 600 RPM. The reactor was cooled to −25° C. and 65.2 grams of TiCl₄was added. After the addition, the stirring rate was dropped to 200 andthe reaction was heated to 35° C. over two hours. Hold for 30 minutes.Heated to 85° C. for 30 minutes. Hold for 30 minutes. Filter. Thereaction was washed with 50 mL of toluene, 3×, JT 80° C., 400 RPM.Filter. 65 ml of toluene was added and the reactor was heated to 40° C.@ 400 RPM. 0.64 grams NPDE1 was added and the reactor was heated up to105° C. and held for one hour. Filter. 65 mL of 10% TiCl₄ was added andthe temperature raised to 105° C. for one hour. Filter. 65 mL of 10%TiCl₄ was added and the temperature raised to 110° C. for 30 minutes andfiltered 3 times. The reactor was washed with 50 mL of hexanes @ 65° C.and 400 RPM 3 times. The product was discharged as a hexane slurry.

TABLE 1 Catalyst components prepared with two organosilicon compoundsand Al(OiPr)3 Component Example Present D10 D50 D90 Span Ti % Mg % NPDE1% Example 1 TEOS 5.81 9.84 14.9 0.928 3.79 17.34 9.83 Example 2Al(OiPr)3, 5.02 8.94 13.8 0.982 3.94 15.76 17.08 Syltherm, TEOS, NPDE1Example 3. Al(OiPr)3, 9.67 14.5 21.5 0.817 4.19 17.64 9.73 Syltherm,TEOS, Example 4 Al—O only 3.85 7.12 13.5 1.356 2.818 18.48 7.41(comparative)

TABLE 2 Catalysts and polymer properties (catalyst components preparedwith two organosilicon compounds and Al(OiPr)3) MFR, Catalyst CE g/ BD,PP PP PP PP Comment on PP component kg/g 10 min XS, % g/cm³ D10 D50 D90Span B/L3 morphology Example 1 65 1.46 3.1 0.397 353 590 1120 1.3 0.66Raspberry shape Example 2 91.2 0.25 1.88 0.443 319 495 915 1.204 0.681Rounded raspberry shape Example 3 54.4 1.84 2.22 0.394 319 617 10811.235 0.682 Grape shape Example 4 51.4 2.86 4.07 0.237 612 1393 20851.057 0.624 Irregular (comparative) morphologyExamples 5-13 illustrate preparing the catalyst components using asupportive donor, ethyl benzoate. (EB)

TABLE 3 Catalyst components prepared with organosilicon compounds andwith supportive donors Example Comments D10 (μ) D50 (μ) D90 (μ) Span Ti% Mg % NPDE1, % Example 5 No epoxy 6.0 10.5 18.3 1.173 3.6 16.16 16.17(Comparative) compound Example 6 Syltherm/ 14.9 24.0 37.2 0.929 3.3617.62 13.5 TEOS = 2/1; EB/MgCl₂ = 0.34 Example 7 Syltherm/ 9.4 18.0 26.60.960 3.26 15.21 11.7 TEOS = 1/1; EB/MgCl₂ = 0.34 Example 8 TEOS; 12.718.6 26.1 0.720 3.71 16.37 14.2 EB/MgCl₂ = 0.34 Example 9 Syltherm/ 8.714.1 19.8 0.788 3.53 16.25 11.7 TEOS = 1/2; EB/MgCl₂ = 0.34 Example 10Syltherm; 3.1 10.5 17.2 1.338 2.96 16.4 11.3 EB/MgCl₂ = 0.34 Example 11TEOS; 6.4 10.2 14.9 0.842 3.16 17.36 10.4 EB/MgCl₂ = 0.26, rpm 300Example 12 TEOS; 8.6 13.6 20.7 .889 3.01 8.56 10.9 EB/MgCl₂ = 0.26, rpm200 Example 13 No 6.9 11.9 18.8 .996 3.06 7.19 11.1 organosiliconcompound, EB Example 14 No 9.8 20.2 33.5 .173 2.52 8.70 10.46(Comparative) organosilicon compound, Phthalic anhydride

TABLE 4 Catalysts and polymer properties (catalyst components preparedwith organosilicon compounds and with supportive donors) (bulk propylenepolymerization) Catalyst CE MFR, BD, PP D50 PP Component kg/g g/10 minXS, % g/ml (μ) Span B/L3 PP morphology Example 5 70.9 0.23 2.89 0.321449 1.178 0.672 Irregular, agglomerated (Comparative) small particlesExample 6 91.7 0.10 2.29 0.383 1087 0.573 0.706 Rounded raspberry shapeExample 7 82.9 0.26 2.28 0.418 836 0.435 0.720 Rounded raspberry shapeExample 8 81.1 0.17 2.40 0.424 899 0.433 0.738 Rounded shape Example 984.3 0.17 3.14 0.454 705 0.704 0.707 Rounded raspberry shape Example 1083.1 0.12 2.23 0.421 970 0.992 0.625 Raspberry shape Example 11 81.90.34 2.44 0.447 492 0.754 0.719 Rounded shape Example 12 79.4 0.2 2.000.425 643 0.736 0.713 Rounded raspberry shape Example 13 75.4 0.07 1.830.410 644 0.626 0.699 Grape shape with small (Comparative) subparticlesExample 14 53.9 0.10 0.127 0.404 772 0.764 — Grape type (Comparative)

Example 5 (Comparative)

The catalyst component was made using tetraethylorthosilicate and thesupportive donor, ethyl benzoate, and without an epoxy compound todissolve MgCl₂. This example demonstrates an irregular polymermorphology with low BD.

MgCl₂ (12.0 g) and hexane (130 g) were combined to form an initialreaction mixture. To the mixture was then added 2-ethylhexanol (50 g)with stirring (600 rpm), and the temperature was then raised to 120° C.This temperature was then maintained for 4 hours. To the reactionmixture was then added tetraethylorthosilicate (1.75 g in 2.0 g ofhexane), and the reaction was held for 20 minutes, followed by coolingto −25° C. At the low temperature, TiCl₄ (150 ml) was added over 1.5hours, after which time the temperature was raised to room temperature.At room temperature ethyl benzoate (2 g in 2 g hexane) was added and themixture heated to 100° C. A NPDE1 (3.0 g in 5 g of toluene) was thenadded and the reaction mixture maintained at 100° C. for 1 hour. Thesolid material was then collected by filtration and it was washed withtoluene (3×200 mL at 85° C. with 10 minute stirrings at temperaturebefore re-filtration). Upon re-suspending the solid in toluene,additional NPDE1 (2.0 g in 5.0 g of toluene) was added at 40° C., andthe solid collected by filtration and washed with hexane. The process ofadding NPDE1, heating at 110° C. (0.5 hours) and filtering was thenrepeated process of washing with hexane and filtering was then repeated3 times. Finally, the solid product was washed with (4×300 ml hexane at65° C.), and the solid discharged to a hexane slurry.

FIG. 1 is a photograph of the polymer obtained from Example 5(Comparative). The images presented are SEM images of polypropyleneparticles produced with the catalysts from the corresponding examples.Because the polymer particles replicate the catalyst particles, we cancompare the catalyst morphology in each example. The catalyst andpolymer morphology are key factors to consider in commercial polymerproduction processes. The polymerization processes require goodflowability of the polymer for transfer of the polymer from one reactorunit to another. The process should operate without producing anypolymer fines that result in a plugging polymerization reactor.Therefore, for any polymerization process the strong and uniformmorphology of the catalyst and high bulk density of polymer ispreferred.

As illustrated in FIG. 1, the polymer morphology of polymer prepared byExample 5 (Comparative) includes small sub-particles. The bulk densityof polymer is very low at 0.321 g/ml. The catalyst and polymer from thisexample are not favored and would result in the plugging reactor by thefines that are generated.

Example 6

Granular supported catalyst component prepared with Syltherm and TEOS(as organosilicon compounds) and ethyl benzoate as supportive electrondonor. The example demonstrates improvement of the catalyst componentwith larger particle size 24 microns and high activity catalyst(catalyst efficiency 92 kg/g) and producing polymer with rounded shape.

MgCl₂ (13.2 g), Al(OCH(CH3)2)3 (1.0 g), toluene (59.5 g),tri-n-butylphosphate (36.3 g), epichlorohydrin (14.25 g), and Syltherm(6.0 g) are combined and heated to 60° C. with agitation at 600 rpm for8 hours under a nitrogen atmosphere. Upon cooling to room temperature,toluene (140 g) was added, along with ethyl benzoate (4.5 g) andtetraethylorthosilicate (3 g). The mixture was then cooled to −25° C.and TiCl₄ (261 g) was slowly added under 600 rpm stirring, whilemaintaining the temperature at −25° C. After the addition was complete,the temperature was maintained for 1 hour prior to warming to 35° C.over 30 minutes, at which temperature it was held for 30 minutes, thenthe temperature was raised to 85° C. over 30 minutes, and held for 30minutes prior to collection of a solid precipitate via filtration. Thesolid precipitate was washed three times with toluene (200 ml, eachwash).

The resulting precipitate was then combined with TiCl₄ in toluene (264ml; 10 vol %). This mixture was heated under agitation to 85° C.,followed by addition of NPDE 1 (2.0 g) in toluene (10 g). Heating at 85°C. was continued for 1 hour prior to collection of the solid viafiltration. This process of combining with TiCl₄ in toluene, heating,adding NPDE 1, was repeated at 95° C. and again at 110° C. beforewashing the final product four times with hexane (200 ml, each wash),and agitating at 60-65° C. for 10 minutes for each wash. The catalystcomponent was then discharged as a hexane slurry. FIG. 2 is a photographof the polymer produced with the catalyst component obtained fromExample 6. Polymer morphology like rounded raspberry shape with largesubparticles.

Example 7

This example produced a granular supported catalyst illustrating high BDcatalyst/PP, with a narrow Span. Example 6 was repeated, however thePDMS was added at 3.0 g, and Al(OCH(CH3)2)3 (0.5 g) and NPDE 1 (2.0 g)was added in toluene wash before the final TiCl₄/Toluene treatment.

Example 8

Example 7 was repeated, however the TEOS was added at 6.0 g and noSyltherm was added. This example produced a granular supported catalystwhich produced polymer with rounded shape morphology (B/L3=0.74)

Example 9

This example produced a granular supported catalyst illustratingimprovement of the catalyst and polymer morphology, and showing high BDcatalyst/PP, with a narrow Span. The polymer is illustrated in FIG. 3.Example 7 was repeated; however the TEOS was added at 1.50 g.

Example 10

Illustrates preparation of catalyst component using Syltherm asorganosilicon silicon compound. Granular supported catalyst componentdemonstrating reduction of particle sizes. Example 7 was repeated,however no TEOS was added.

FIGS. 2 and 3 illustrate the rounded raspberry type morphology ofpolymers prepared by the catalysts of Examples 7, and 9, respectively,using an epoxy compound to dissolve MgCl₂, along with varyingcombinations of organosilicon compounds (polydimethoxysilane (PDMS) andtetraethoxysilane (TEOS)), and ethyl benzoate, demonstrate improvementin catalyst and polymer morphology. The FIGS. 2 and 3. show thematerials as having a well-defined morphology. The large sub-particlesare associated in large particles. The polymers produced with thesecatalysts exhibit a high density (>0.40 g/ml) and sphericity (B/L3>0.71)(see tables above).

Example 11

Demonstrates effect of amount of supportive donor on catalyst componentparticle size. Example 8 was repeated except amount of ethyl benzoatewas reduced from 0.34 g/gMgCl₂ to 0.26 g/gMgCl₂ which resulted in areduction of the catalyst component particle size from 18.6 microns to10.2 microns.

FIG. 4 the rounded shape of polymer morphology produced by the catalystfrom Example 11.

Example 12

Demonstrates effect of agitation speed during the precipitation of thecatalyst component on catalyst component particle size. Example 11 wasrepeated except the agitation speed was reduced from 300 rpm to 200 rpm,which resulted in increasing catalyst component particle size from 10.2microns to 13.6 microns

Example 13. (Comparative)

Granular supported catalyst demonstrating reduction of particle sizesand bulk density of the catalyst and polymer. No Al(OCH(CH3)2)3,Syltherm, or TEOS was used. Example 7 was repeated, however noAl(OCH(CH3)2)3, PDMS, or TEOS was added. Example 13 demonstrates thatperformance of the catalyst component prepared by using an epoxycompound to dissolve the MgCl₂, and using only ethyl benzoate as asupportive donor without using organosilicon compounds. FIG. 5represents the morphology of polymer produced according to Example 13.Each polymer particle contains numerous small sub-particles. In somepolymerization processes, this morphology is not favored because theseparticles can be easily disintegrated up during the polymerizationprocess.

Example 14. (Comparative)

Catalyst component made with phthalic anhydride as a precipitationagent. The catalyst component contains bis(1,3-dichloro-iso-propyl)phthalate (1.2%) and phthaloyl chloride (0.3%) as a reaction product ofphthalic anhydride with TiCl₄ and Mg-compounds during the catalystcomponent preparation. The catalyst component shows lower catalystactivity than the catalyst produced under the current claims. Thepolymer particle morphology is a grape type with B/L3<0.70.

MgCl₂ (13.2 g), toluene (190.0 g), tri-n-butylphosphate 26.6 g), ECH(25.6 g) were combined and heated to 60° C. with agitation at 600 rpmfor 8 hours under a nitrogen atmosphere. Phthalic anhydride was added(4.6 g) at 60° C. The mixture was then cooled to −25° C., at whichtemperature TiCl₄ (260 g) was slowly added with 600 rpm agitation. Thetemperature was maintained for 1 hour, followed by raising thetemperature to 10° C. over 30 minutes, holding for 30 minutes, raisingto 85° C. over 70 minutes, and holding for 15 minutes before collectingthe solid via filtration. The solid was washed three times with toluene(200 ml) for 10 minutes each at the 85° C. The solid was then collectedby filtration and washed with toluene (265 ml). After filtration, theTiCl₄/toluene solution and NPDE 1 (3.0 g) in toluene (2 g), was addedand heated at 105° C. After again filtering, the solid was collected,and washed with the TiCl₄/toluene solution at 110° C. under agitation.Finally, the solid was washed with hexane (200 ml) four times underagitation at 60-65° C., with the catalyst being discharged as a hexaneslurry. The catalyst of Example 14 demonstrates lower catalyst activitythan the catalyst prepared without phthalic anhydride.

Examples 15-17 illustrate the catalyst component preparation using TEOSas organosilicon compound and ethyl benzoate as a supportive electrondonor. Examples 18-23 illustrate the polymerization data in bulkpropylene and gas phase reactors producing polymer with substantiallyspherical shape.

Example 15

Example of 11 was repeated in a scale of MgCl₂=20 kg

Example 16

Add 13.2 g MgCl₂, 0.5 g Al(OR)3, 72 g toluene, 25.7 g ECH, 26.8 g TBP,Heat and Agitate at 60 C/600 rpm/8 hr. Cool down to 25 C. Leave for nextday under N2 Blanket. Add 75.0 g toluene, 3.5 g EB in 12 g toluene, 6.0g TEOS in 8 g toluene @ 25 C. Cool to −25 C @ 600 rpm and add 260.8 gTiCl₄ slowly addition. Raise from −25 C to 35 C over 2 hr @ 350 rpm andhold at 35 C for 30 min/350 rpm. Raise from 35 C to 85 C in 30 min andhold at 85 C for 30 min @ 350 rpm filter. Wash w/200 ml toluene/3×/10min & add 200 ml toluene leave under N2 Blanket Next day & Filter. Add265 ml of Toluene heat, add 1.25 g of NPDE1, heat 105° C. 400 rpm 1 hr.Filter, 1st Act add 265 ml 10% TiCl₄/tol heat to 105 C/400 rpm/1 hr andfilter From the 2nd Act to 4th Act, add 265 ml 10% TiCl₄/tol heat to 110C/400 rpm/30 minutes and filter Wash w/200 ml of hexane @ 65 C JT/4×/10min & discharge as hexane slurry

Example 17

Example 15 was repeated with increasing the NPDE1 amount by 10%

TABLE 5 Catalyst Component Comment D10 D50 D90 Span Ti % Mg % NPDE1 %Example TEOS, EB (20 kg of 8.8 11.6 15.4 0.570 3.04 16.85 10.68 15 MgCl₂scale) Example ECH/MgCl₂ = 2 (mol); 11.5 17.5 26.4 0.851 2.95 16.8810.54 16 TEOS, EB Example TEOS, EB (20 kg of 6.19 11.4 18.1 1.044 2.5616.64 10.37 17 MgCl₂ scale)

TABLE 6 Poly- MFR, Catalyst merization CE g/10 XS, BD, PP PP PP PP PPExample Component condition kg/g min % g/cm³ D10 D50 D90 Span B/L3morphology Example From Bulk 70.6 1.36 2.40 0.463 490 717 1698 1.6850.706 Rounded 18 example 15 shape Example From Gas Phase 64.3 4.20 2.150.436 443 511 672 0.447 0.797 Substantially 19 example 15 sphericalshape Example From Bulk 93.6 0.26 2.25 0.432 706 848 1107 0.473 0.762Rounded 20 example 16 Shape Example From Gas Phase 63.9 1.70 1.94 0.389645 756 919 0.363 0.782 Substantially 21 example 16 spherical shapeExample From Bulk 90.1 0.33 2.04 0.435 446 558 843 0.711 0.763Substantially 22 example 17 spherical shape Example From Gas Phase 60.61.4 1.89 0.414 423 508 716 0.575 0.763 Substantially 23 example 17spherical shape

Examples 18-23 demonstrate production polymer in bulk and gas phasepolymerization reactors with substantially spherical shape of particleswith B/L3 of 0.8. FIG. 6 shows PP with substantially spherical shapemorphology (microspheres) from example 23.

Surface area (BET) measurement and porosity of the catalyst componentsshow surface area of around 400 m2/g.

TABLE 7 Surface area (BET) Catalyst SA, Ads Des Ads Des component BET,m²/g PV, cm³/g PV, cm³/g PD, A PD, A Example 23 395.0 0.2714 0.271927.4841 27.5313

Examples 24-27 illustrate the relationship of the catalyst performancesand relatively ratio of supportive electron donor and internal electrondonor. The catalyst isotacticity reduces (% XS) with increasing EB/NPDE1ratio but the catalyst activity does not change sufficiently.

TABLE 8 Analytical data for catalyst components and correspondingcatalyst polymerization data with variable ratio of supportive electrondonor and electron donor NPDE1/ MgCl2, NPDE1, EB, CE MFR, XS, Example wtTi, % Mg % % % kg/g g/10 min % Example 24 0.227 3.37 18.62 13.06 6.03102.3 0.16 2.21 Example 25 0.182 3.37 16.93 10.70 7.46 93.7 0.14 2.53Example 26 0.152 3.57 17.15 9.34 8.50 91.6 0.35 3.07 Example 27 0.1213.62 16.7 7.73 9.90 96.3 0.35 3.87

Catalyst components in Examples 24 through 27 were produced as inExample 8 except the amount of NPDE1 was used as in Table 8. Catalystcomponent particle sizes are 32 microns (produced with agitation speedof 200 rpm during the support precipitation).

Example 28 illustrates granular catalyst components prepared with NPDE2as an internal donor diaryl ester and example 29 presents polymerizationdata in bulk propylene.

Example 28

Example 8 was repeated except NPDE2 was used as internal electron donor(NPDE2/MgCl₂=0.18 (wt)

The catalyst component was tested in bulk propylene polymerization toevaluate the hydrogen response on MFR.

TABLE 8 Analytical data for catalyst components with NPDE 2 Ti Mg DConditions D10 D50 D90 Span % % % Example 28 NPDE2, 11.2 18.8 28.9 0.9403.53 17.12 n/a TEOS

TABLE 9 Polymerization data using catalyst component from example 28Catalyst H2, CE MFR, XS, BD, PP PP PP PP component SL kg/g g/10 min %g/cm³ D10 D50 D90 Span B/L3 Example From 5 94.7 1.5 3.36 0.424 762 9861604 0.854 0.696 29 example 28

As shown above, Example 29 was conducted at a hydrogen concentration of5 SL. In general, the hydrogen concentration can be from about 5 SL toabout to 40 SL or higher. In general, at lower hydrogen concentrations,such as less than about 20 SL, such as less than about 10 SL, polymersare produced having a relatively low melt flow rate. For instance, themelt flow rate can be less than about 8 g/10 min, such as less thanabout 5 g/10 min, such as less than about 3 g/10 min, such as less thanabout 2 g/10 min, such as less than 1 g/10 min, and generally greaterthan about 0.01 g/10 min. At higher hydrogen amounts, such as greaterthan about 30 SL, such as from about 30 SL to about 50 SL, the melt flowrate can be dramatically increased. For instance, the melt flow rate canbe greater than about 100 g/10 min, such as greater than about 150 g/10min, such as greater than about 200 g/10 min, such as greater than about250 g/10 min, such as greater than about 300 g/10 min, such as greaterthan about 350 g/10 min, such as greater than about 400 g/10 min, suchas greater than about 450 g/10 min, such as greater than about 500 g/10min, and generally less than about 800 g/10 min.

Hydrogen concentration can have some impact on catalyst activity. Ingeneral, the catalyst activity can range from about 90 kg/g to about 200kg/g. A catalyst activity of from about 150 kg/g to about 200 kg/g canreflect a flat kinetic profile.

Hydrogen concentration generally does not impact bulk density orparticle size. For instance, the bulk density can be greater than about0.3 g/cc, such as greater than about 0.35 g/cc, such as greater thanabout 0.4 g/cc, and generally less than about 0.5 g/cc, such as lessthan about 0.45 g/cc. The D50 particle size can generally be from about500 microns to about 1700 microns, and generally from about 800 micronsto about 1400 microns. The B/L3 of the polymer can generally be greaterthan about 0.6, such as greater than about 0.65 and generally less thanabout 0.8, such as less than about 0.75.

Examples 30-32 illustrate preparing the catalyst components using 1,3diether (3,3-bis(methoxymethyl)-2,6-dimethylheptane) (DEMH) as aninternal donor.

Example 30

Added 6.6 g MgCl₂, 0.5 g Al(O-iPr)3, 48 g toluene, 18.2 g TBP, 7.1 g ECHto reactor. Heated and agitated at 60° C./600 rpm/8 hr. Cooled down to25 C. Added 35 g toluene, 2.25 g ethyl benzoate in 5 g toluene, 3.0 gTEOS in 5 g toluene and 0.75 g of DEMH in 5 g of toluene @ 25 C. Cooledto −25 C @ 600 rpm and added 130.4 g TiCl₄ slowly addition. Raised from−25 C to 35 C over 2 hr @ 250 rpm and held at 35 C for 30 min/250 rpm.Raised from 35 C to 85 C in 30 min, held for 1 hour and filtered off.Washed w/100 ml toluene/3×/10 min. Added 132 ml of 10% TiCl₄/toluene,added (1.25 g of DEMH in 5 g of toluene @ 40 C. heat at 80 C for 1 h,filtered off. Added 132 ml of 10% TiCl₄/tol and heated at 105 for 1hour. The treatment was repeated at 110° C. for 30 min three more times.The solid was washed with hexane and discharged as a hexane slurry.

Example 31

Example 8 was repeated except the solid precipitation was conducted at350 rpm agitator speed and 0.80 g of DEMH used as an internal donor with15% TiCl₄/toluene treatment.

Example 32

Example 9 was repeated except the catalyst treatment was conducted with20% TiCl₄/toluene.

TABLE 10 Catalyst component characterization (1,3 diether(3,3-bis(methoxymethyl)-2,6-dimethylheptane) (DEMH) DEMH, CE MFR, XS,BD, PP PP D50 Span Ti % Mg % % kg/g g/10 min % g/cm³ D50 Span B/L3 PPmorphology Example 18.4 1.014 19.2 76.2 8.5 1.24 0.407 835 0.620 0.736Substantially 30 spherical shape Example 10.8 0.525 2.66 18.03 12.2 74.66.8 0.424 710 1.244 0.672 Rounded 31 raspberry shape Example 11 0.5472.92 17.84 12.9 98.0 5.1 2.83 0.437 616 1.268 0.688 Rounded 32 raspberryshape

Example 33

Demonstration of the preparation and performance of the sphericalcatalyst component. MgCl₂ (13.2 g), Al(OCH(CH3)2)3 (1.0 g), toluene(59.5 g), tri-n-butylphosphate (“TBP;” 36.3 g), ECH (14.25 g), andSyltherm (6.0 g) are combined and heated to 60° C. with agitation at 600rpm for 8 hours under a nitrogen atmosphere. Upon cooling to roomtemperature hexane (59.0 g), dibutyl ether (8 g in 13 g hexane),Viscoplex (6.0 g) in hexane (40 g), and EB (4.5 g) in hexane (5 g) weremixed and cooled to 0° C., at which temperature TiCl₄ (288 g) was slowlyadded with 600 rpm agitation. The temperature was maintained for 1 hour,followed by raising the temperature to 10° C. over 30 minutes, holdingfor 30 minutes, raising to 85° C. over 70 minutes, and holding for 15minutes before collecting the solid via filtration. The solid was washedthree times with toluene (200 ml) for 10 minutes each at the 85° C. Thesolid was then collected by filtration and washed with a 10 wt %TiCl₄/toluene solution (265 ml) with agitation at 85° C., followed byaddition of NPDE1 (2.0 g) in toluene (5.0 g) with heating at 85° C. for60 minute, and followed by filtration. After filtration, the solid wasagain washed with the TiCl₄/toluene solution and NPDE1 (0.5 g) intoluene (2 g), but this time at 95° C. After again filtering, the solidwas collected, and washed with the TiCl₄/toluene solution at 110° C.under agitation. Finally, the solid was washed with hexane (200 ml) fourtimes under agitation at 60-65° C., with the catalyst being dischargedas a hexane slurry.

Example 34 demonstrates the preparation of a spherical catalystcomponent made using epoxy compounds to dissolve MgCl₂, but without theuse of an anhydride. Instead, an organosilicon compound, Al(O-iPr)3, andethyl benzoate were used. The polymer produced with this catalyst (FIG.7) shows high density particles and good sphericity (microspheres).

Example 35

Demonstration of the preparation and performance of the sphericalcatalyst component using TEOS instead Syltherm. Example 34 was repeated,however the Syltherm was replaced with TEOS (5 g) and dibutyl ether (12g) was used.

Example 36 (Comparative)

A catalyst was made with EB (no PDMS, no aluminum alkoxide)demonstrating irregular catalyst/polymer morphology, low BD ofcatalyst/polymer and broad catalyst/PP span. Example 33 was repeated,however no PDMS and Al(OCH(CH3)2)3 were added. Example 35 demonstratesthe preparation of a catalyst component, prepared using an epoxycompound to dissolve MgCl₂, and ethyl benzoate. No organosiliconcompounds and Al(O-iPr)3 were used. The polymer produced with thecatalyst of Example 35, exhibits low bulk density particles and with anirregular morphology.

TABLE 11 Analytical Data for the spherical solid catalyst components andpolymer properties Example 34 35 36 (Comp.) D10 (μ) 12.6 16.9 8.6 D50(μ) 20.7 27.2 28.8 D90 (μ) 34.7 44.2 60.2 Span 1.069 1.004 1.792 Ti %1.77 2.31 2.65 Mg % 16.23 18.50 17.23 NPDE1, % 12.9 12.5 11.3 CE kg/g66.4 58.6 67.1 MFR, 0.12 0.73 0.22 g/10 min XS, % 1.12 1.49 1.60 BD,g/ml 0.439 0.390 0.387 PP D50 827 1098 957 (μ) PP Span 0.912 0.808 1.325

Because polymer morphology is a replica of the catalyst morphology, thesame trends in the catalyst morphology are expected. The catalyst andpolymer morphology are key factors to consider in any commercial polymerproduction process. It is known that some polymerization processesrequire good flowability of the polymer, or transfer of the polymer fromone reactor unit to another.

The catalysts/methods lead to the production of poly-α-olefins having aa variable molecular weight distribution. Polydispersity Index (PI) isstrictly connected with the molecular weight distribution of thepolymer.

Examples 37-39 demonstrate properties of polypropylene (PI andrheological breadth) produced with catalyst components using differentinternal donors

TABLE 12 PI and phelogical breadth of PP produced with selectedcatalysts Rheological Example Catalyst Internal donor PI Breadth Example37 Catalyst based NPDE1 5.2559 0.2754 on example 8 Example 38 Catalystbased NPDE1 6.1586 0.2892 on example 8 Example 39 Catalyst based DEMH3.8113 0.3912 on example 31

Example 40-43

The solid catalyst component from example 11 was used for bulk propylenepolymerization as described above except a mixture of external donorssold under the designation D6500 were used, which are commerciallyavailable from W.R. Grace and Company. The table below demonstrateseffect of amount of a mixture of external donors on XS level (catalystactivity) and polymer properties.

TABLE 13 Corr MFR, PP Catalyst Donor CE g/ XS, D50, Example Component(ml) kg/g B/D 10 min % microns Span b/l3 Example Example 0.39 108.80.411 2.46 5.53 1698 1.042 0.596 40 15 Example Example 0.78 96.8 0.4390.73 3.27 716 1.094 0.695 41 15 Example Example 1.17 85.6 0.446 0.912.25 562 0.859 0.751 42 15 Example Example 1.56 91.6 0.429 1.25 1.99 5630.917 0.751 43 15

The solid catalyst components or the solid precipitates can be used forethylene polymerization process. Example 44 demonstrates catalystactivity and polyethylene properties produced with solid precipitatefrom example 15. The polymerization was conducted in hexane in aone-gallon reactor. The reactor was purged at 100° C. under nitrogen forone hour. At room temperature, 0.6 ml of 25-wt % triethylaluminum (TEA1)in heptane was added into the reactor. Then 1500 ml of hexane was addedand 10 mg of the catalyst prepared above were added into the reactor.The reactor was pressurized with H2 to 60.0 psig then charged withethylene to 116 psig. The reactor was heated to and held at 80° C. fortwo hours. At the end of the hold, the reactor was vented and thepolymer was recovered.

TABLE 14 Ethylene polymerization with the solid component Ti, Mg, CE,BD, MFI PE Example D50 % % kg/g g/cm³ MFI2 MFI10 MFI22 Ratio D50 SpanExample 44 12 4.45 15.84 35.2 0.303 1.918 17.205 72.484 37.791 330 0.883

Examples 45 and 46 demonstrate the improved lifetime of catalysts madein accordance with the present disclosure.

The lifetime of polymerization catalysts can be important for thecommercial production of polyolefins. The long lifetime of the catalystallows to conduct polymerization processes continually in differentreactors producing homopolymers and co-polymers with a variety ofproperties. Many Ziegler-Natta catalysts, in particular non-phthalatedonor catalysts, have a limited lifetime. Usually the catalyst activityfor these types of catalysts is very high at the beginning of thepolymerization process and decreases dramatically thereafter. In two orthree reactor polymerization processes, these catalysts are not usefuldue to low catalyst activity after the first reactor polymerization. Thedecay of the catalyst activity is related to deactivation of activecenters on the catalyst surface.

Catalyst systems made in accordance with the present disclosure weretested for catalyst lifetime. In particular, the kinetics of thecatalysts were evaluated after 1 hour (45 minutes) and after 2 hours(105 minutes) to determine the difference in catalyst activity over theentire period of time.

The following catalysts were prepared.

Example No. 45

The catalyst was prepared as described in Example No. 34.

Example No. 46

Add 3.3 g TOHO MgCl2, 0.125 g Al(O-iPr)3, 3.55 g ECH, 9.1 g TBP, 15 gtoluene, 0.75 g Syltherm in serum bottle. Agitate at 60 C/600 rpm/8 hr+.Cool down to 25 C. Leave for next day under N2 Blanket. Add 27 gtoluene, 1.12 g ethyl benzoate in 3 g toluene, 0.75 g TEOS in 3 gtoluene @ 25 C. Cool to −25 C @ 600 rpm and add 65.2 g TiCl4 slowly.Raise from −25 C to 35 C over 30 min @ 300 rpm. Hold at 35 C for 30min/300 rpm. Raise from 35 C to 85 C in 30 min and hold at 85 C for 30min @ 300 rpm. Wash with 50 ml toluene 3× at 400 rpm for 10 min @80 CJT. Filter. Next day. Add 65 ml 10% TiCl4/toluene to rx/400 rpm. Add(0.25 g NPDE in 2 g toluene) at 70 C. Heat to 85c. Hold and agitate at85 C/1 hr/400 rpm. Filter. Act1=65 ml 10% TiCl4/tol and (0.5 g NPDE in 2g toluene @70 C). Hold at 95 C/1 hr; Act2=65 ml 10% TiCl4/tol at 110C/30 min; Act3=65 ml 10% TiCl4/tol at 110 C/30 min; Act4=65 ml 10%TiCl4/tol at 110 C/30 min; wash with 50 ml hexane/400 rpm at 65 CJT/agitate 5 min(4×); discharge as hexane slurry.

The above catalysts were then used to produce polypropylene polymers.

A reactor was baked at 100° C. under nitrogen flow for 30 minutes priorto the polymerization run. The reactor was cooled to 30-35° C. andcocatalyst (1.5 ml of 25 wt % triethylaluminum (TEA1)), C-donor[cyclohexylmethydimethoxysilane] (1 ml), hydrogen (3.5 psi) and liquidpropylene (1500 ml) were added in this sequence into the reactor. Thecatalyst (5-10 mg), loaded as a mineral oil slurry, was pushed into thereactors using high pressure nitrogen. The polymerization was performedfor one or two hours at 70° C. After the polymerization, the reactorswere cooled to 22° C., vented to atmospheric pressure, and the polymercollected.

The following results were obtained:

MFR Example Run CE B/D g/ XS D-50 Split 1st & No. time kg/g g/cm³ 10 min(%) (Microns) Span b/l3 2nd hs (%) 45 60 69.3 0.444 0.24 1.36 793 0.8390.815 55.4 45 120 125.2 0.447 0.49 1.84 1009 0.816 0.822 44.6 46 60 82.20.417 0.18 2.21 824 0.501 0.720 55.4 46 120 148.3 0.416 0.62 2.53 10180.474 0.723 44.6

As shown above, the catalysts made according to the present disclosurehave excellent catalyst activity during the entire two hour period ofpolymerization. More particularly, the data illustrates that catalystsystems in accordance with the present disclosure have an extendedlifetime such that the catalyst activity during a second hour ofpolymerization is not less than about 8%, such as not less than about 7%of the catalyst activity of the catalyst system during a first hour ofpolymerization.

Examples 47-51

The following examples were conducted in order to demonstrate thedramatic and unexpected improvement in the flowability or polymers madeaccording to the present disclosure. In particular, the followingexamples demonstrate the improved flowability properties of elastomericpropylene-ethylene copolymers made in accordance with the presentdisclosure that contain relatively high amounts of amorphouspolyethylene that provide the polymers with elastomeric properties. Theexamples below, for instance, had a rubber content of greater than 30%by weight. Such polymer resins typically have very poor flow propertiesand have a tendency to stick together and form agglomerates.

The propylene-ethylene random copolymers were formed using a gas phasepolymerization process. The reactor set up included two fluidized bedreactors in series. Polypropylene homopolymer was produced in the firstreactor. Non-phthalate catalysts were used to produce the polymers.Example numbers 47 and 48 below are comparative examples. In theseexamples, a commercially available catalyst sold under the name CONSISTAand available from the W.R. Grace & Co. was used. In Example numbers49-51, however, a catalyst was made in accordance with Example No. 8above except a scale of 20 kg was used.

In the first reactor, the catalyst was used in conjunction withtriethylaluminum as a cocatalyst. A mixed external electron donor wasalso used. In Examples 47 and 48, the mixed external electron donorsincluded dicyclopentyldimethoxysilane (DCPDMS) as the selectivitycontrol agent and iso-propylmyristate (IPM) as the activity limitingagent. In Example numbers 49-51, the mixed external election donorsincluded n-propyltrimethoxysilane (NPTMS) as the selectivity controlagent and pentyl valerate (PV) as the activity limiting agent.

The homopolymer powder produced in the first reactor was passed to thesecond reactor where the gas phase contained ethylene and propylene. Thepowder was held in the second reactor for a residence time long enoughto produce a powder with an ethylene/propylene rubber content ofapproximately 31 weight %.

The reactor set up was a two gas phase fluidized-bed UNIPOL reactorsystem available for license by W.R. Grace & Co. and is described inU.S. Pat. No. 4,882,380, which is incorporated herein by reference.

After the propylene-ethylene copolymers were produced, the polymerresins were tested according to the Cup Test as described above. Thefollowing Table includes operating conditions, product information, andthe Cup Test results.

Example 47 Example 48 Example 49 Example 50 Example 51 Rx1 Donor 80/2080/20 90/10 90/10 90/10 Composition IPM/DCPDMS IPM/DCPDMS PV/NPTMSPV/NPTMS PV/NPTMS Rx2 60/40 60/40 60/40 60/40 60/40 AntifoulantIPM/NPTMS IPM/NPTMS IPM/NPTMS IPM/NPTMS IPM/NPTMS Composition Rx1 MF29.5 44.2 63.7 64.2 63.8 (g/10 min) Rx1 XS Wet 1.78 1.73 1.71 1.66 1.62(wt %) Rx1 60870 56757 25577 27143 27708 Productivity- XRF (lb/lb) Rx1Temp 71.9 72.1 72.0 72.0 72.0 (° C.) Rx1 C3PP 319.9 320.0 318.7 319.5319.7 (psia) Rx1 Bed Wt 50.5 53.0 50.9 48.9 49.2 (lb) Rx1 FBD 8.0 8.27.3 7.2 7.2 (lb/ft3) Rx1 SBD 20.5 22.5 18.4 17.9 17.9 (lb/ft3) Rx1 APS0.0167 0.0166 0.0175 0.0172 0.0209 (inch) Rx1 Fines 9.1 11.0 6.2 7.3 4.1(wt %) Rx1 Al 26 22 25 26 28 (ppmw) Rx1 Ti 0.69 0.74 1.04 0.98 0.96(ppmw) GRADEX 0.00 0.00 0.00 NT 0.09 Rx1 10 Mesh (wt %) GRADEX 3.29 3.920.63 NT 2.82 Rx1 18 Mesh (wt %) GRADEX 26.73 26.32 36.25 NT 49.44 Rx1 35Mesh (wt %) GRADEX 43.25 40.72 41.48 NT 33.27 Rx1 60 Mesh (wt %) GRADEX17.58 18.08 15.47 NT 10.24 Rx1 120 Mesh (wt %) GRADEX 5.42 5.52 4.61 NT2.82 Rx1 200 Mesh (wt %) GRADEX 3.73 5.44 1.56 NT 1.32 Rx1 Pan (wt %)Rx1 SCA in 86 74 48 109 97 resin ppm Rx2 MF 18.93 28.66 22.27 22.3321.07 (g/10 min) Rx2 Temp 65 65 70 70 70 (° C.) Rx2 C3 PP 182.0 167.9137.5 119.0 121.3 (psi) SCA2/ 0.44 0.38 0.15 0.15 0.15 SCA1 Rx2 Bed Wt87 91 83 84 85 (lb) Rx2 FBD 12.87 13.02 11.92 12.45 12.53 (lb/ft3) Rx2SBD 17.9 18.4 16.7 16.7 15.6 (lb/ft3) Rx2 APS 0.046 0.044 0.038 0.0340.036 (inch) Rx2 Fines 0.08 0.09 0.22 0.40 0.40 (wt %) Rx2 Ti 0.45 0.380.73 0.77 0.81 (ppmw) Rx2 Al 21 19 34 26 28 (ppmw) Rx2 10 Mesh 5.52 4.192.01 NT 2.92 (wt %) Rx2 18 Mesh 50.53 49.77 36.06 NT 29.08 (wt %) Rx2 35Mesh 38.77 38.05 52.34 NT 50.73 (wt %) Rx2 60 Mesh 5.11 7.81 9.07 NT16.20 (wt %) Rx2 120 0.00 0.09 0.30 NT 0.66 Mesh (wt %) Rx2 200 0.080.00 0.22 NT 0.27 Mesh (wt %) Rx2 Pan 0.00 0.09 0.00 NT 0.13 (wt %) Fc(wt %) 33.2 31.0 34.6 31.8 31.3 Ec (wt %) 41.1 41.7 41.9 39.8 40.2 Et(wt %) 13.6 12.9 14.5 12.7 12.6 30 Minute 42 34 9 7 8 Cup Test Score(seconds)

As shown above, propylene-ethylene copolymers made in accordance withthe present disclosure had dramatically reduced Cup Test Times incontrast to the comparative examples.

While certain embodiments have been illustrated and described, it shouldbe understood that changes and modifications can be made therein inaccordance with ordinary skill in the art without departing from thetechnology in its broader aspects as defined in the following claims.

The embodiments, illustratively described herein may suitably bepracticed in the absence of any element or elements, limitation orlimitations, not specifically disclosed herein. Thus, for example, theterms “comprising,” “including,” “containing,” etc. shall be readexpansively and without limitation. Additionally, the terms andexpressions employed herein have been used as terms of description andnot of limitation, and there is no intention in the use of such termsand expressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the claimed technology.Additionally, the phrase “consisting essentially of” will be understoodto include those elements specifically recited and those additionalelements that do not materially affect the basic and novelcharacteristics of the claimed technology. The phrase “consisting of”excludes any element not specified.

The present disclosure is not to be limited in terms of the particularembodiments described in this application. Many modifications andvariations can be made without departing from its spirit and scope, aswill be apparent to those skilled in the art. Functionally equivalentmethods and compositions within the scope of the disclosure, in additionto those enumerated herein, will be apparent to those skilled in the artfrom the foregoing descriptions. Such modifications and variations areintended to fall within the scope of the appended claims. The presentdisclosure is to be limited only by the terms of the appended claims,along with the full scope of equivalents to which such claims areentitled. It is to be understood that this disclosure is not limited toparticular methods, reagents, compounds compositions or biologicalsystems, which can of course vary. It is also to be understood that theterminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting.

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, particularly in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” “greater than,” “less than,” and the like,include the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember.

All publications, patent applications, issued patents, and otherdocuments referred to in this specification are herein incorporated byreference as if each individual publication, patent application, issuedpatent, or other document was specifically and individually indicated tobe incorporated by reference in its entirety. Definitions that arecontained in text incorporated by reference are excluded to the extentthat they contradict definitions in this disclosure.

What is claimed is:
 1. A polymer composition comprisingpropylene-ethylene copolymer particles including propylene as a primarymonomer, the propylene-ethylene copolymer particles comprising ethylenein an amount greater than 3% by weight, the propylene-ethylene copolymerexhibiting a melt flow rate according to ASTM D1238 at 230° C. and aweight of 2.16 kg, of about 50 g/10 min to about 500 g/10 min, andwherein the propylene-ethylene copolymer particles exhibit a Cup TestIndex of 2 or less.
 2. The polymer composition of claim 1, wherein thepropylene-ethylene copolymer contains ethylene in an amount greater thanabout 8% by weight.
 3. The polymer composition of claim 1, wherein thepropylene-ethylene copolymer contains ethylene in an amount greater thanabout 10% by weight.
 4. The polymer composition of claim 1, wherein thepropylene-ethylene copolymer particles exhibit a Cup Test time of lessthan 10 seconds.
 5. The polymer composition of claim 1, wherein thepropylene-ethylene copolymer includes a first polymer phase combinedwith a second polymer phase comprising an elastomeric propylene-ethylenecopolymer.
 6. The polymer composition of claim 1, wherein thepropylene-ethylene copolymer particles have a D50 particle size of fromabout 300 microns to about 3000 microns and have a bulk density of fromabout 0.4 g/cm³ to about 0.6 g/cm³.
 7. The polymer composition of claim1, wherein the propylene-ethylene copolymer is produced in the presenceof a catalyst system, the catalyst system comprising a solid catalystcomponent combined with an aluminum compound, at least one selectivitycontrol agent, and optionally an activity limiting agent, the solidcatalyst component comprising a reaction product of a magnesium compoundwith an epoxy compound, the solid catalyst component further comprisingan organic phosphorus compound, a titanium compound, an organosiliconcompound, and an internal electron donor.
 8. The polymer composition ofclaim 1, wherein the propylene-ethylene copolymer is produced in thepresence of a catalyst system comprising a solid catalyst componentcombined with an aluminum compound, at least one selectively controlagent, and optionally an activity limiting agent, the solid catalystcomponent comprising: magnesium compound including a halide-containingmagnesium compound and a reaction product of a magnesium compound withan epoxy compound; an organic phosphorus compound; a titanium compound;an organosilicon compound; an internal electron donor, the internalelectron donor comprising an aryl diester, a diether, a succinate, anorganic acid ester, a polycarboxylic acid ester, a polyhydroxy ester, aheterocyclic polycarboxylic acid ester, an inorganic acid ester, analicyclic polycarboxylic acid ester, a hydroxy-substituted carboxylicacid ester compound having 2 to 30 carbon atoms, or a compound having atleast one ether group and at least one ketone group, or mixturesthereof; wherein the solid catalyst component is free of side reactionproducts between a carboxylic acid or an anhydride thereof and amagnesium compound or a titanium compound.
 9. The polymer composition ofclaim 1, wherein the propylene-ethylene copolymer is produced in thepresence of a catalyst system that has an extended lifetime such that acatalyst activity of the catalyst system during a second hour ofpolymerization is no less than about 8% of a catalyst activity of thecatalyst system during a first hour of polymerization.
 10. A polymercomposition comprising particles of polypropylene homopolymer,polypropylene copolymer, or a mixture thereof, wherein the particleshave a D50 particle size of about 150 microns to about 3000 microns, theparticles exhibit an aspect ratio, B/L3, of greater than about 0.6, andwherein the polymer composition exhibits a bulk density of greater than0.415 g/cm³; wherein the polypropylene homopolymer or polypropylenecopolymer exhibits a melt flow rate according to ASTM D1238 at 230° C.and a weight of 2.16 kg from 50 g/10 min to 500 g/10 min; and whereinthe particles comprise microspheres.
 11. The polymer composition ofclaim 10, wherein the particles have a B/L3 of from about 0.7 to about1.0.
 12. The polymer composition of claim 10, wherein the polymercomposition has a bulk density of from 0.42 g/cm³ to 0.60 g/cm³.
 13. Thepolymer composition of claim 10, wherein the polypropylene polymer isproduced in the presence of a catalyst system, the catalyst systemcomprising a solid catalyst component combined with an aluminumcompound, at least one selectivity control agent, and optionally anactivity limiting agent, the solid catalyst component comprising areaction product of a magnesium compound with an epoxy compound, thesolid catalyst component further comprising an organic phosphoruscompound, a titanium compound, an organosilicon compound, and aninternal electron donor.
 14. The polymer composition of claim 13,wherein the solid catalyst component further comprises a supportivedonor, the supportive donor comprising a mono aryl ester, the internalelectron donor is represented by one of the following formulas:

wherein: each of R¹ through R³⁴ is independently H, F, Cl, Br, I, alkyl,cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and q is an integerfrom 0 to
 12. 15. The polymer composition of claim 10, wherein thepolypropylene polymer comprises a polypropylene homopolymer.
 16. Thepolymer composition of claim 10, wherein the polypropylene polymercomprises a propylene-ethylene copolymer.
 17. The polymer composition ofclaim 16, wherein the polypropylene polymer comprises a heterophasicrandom copolymer.
 18. The polymer composition of claim 10, wherein thepolypropylene polymer is produced in the presence of a catalyst system,the catalyst system comprising a solid catalyst component combined withan aluminum compound, at least one selectively control agent, andoptionally an activity limiting agent, the solid catalyst componentcomprising: magnesium compound including a halide-containing magnesiumcompound and a reaction product of a magnesium compound with an epoxycompound; an organic phosphorus compound; a titanium compound; anorganosilicon compound; an internal electron donor, the internalelectron donor comprising an aryl diester, a diether, a succinate, anorganic acid ester, a polycarboxylic acid ester, a polyhydroxy ester, aheterocyclic polycarboxylic acid ester, an inorganic acid ester, analicyclic polycarboxylic acid ester, a hydroxy-substituted carboxylicacid ester compound having 2 to 30 carbon atoms, or a compound having atleast one ether group and at least one ketone group, or mixturesthereof; wherein the solid catalyst component is free of side reactionproducts between a carboxylic acid or an anhydride thereof and amagnesium compound or a titanium compound.